Product comprising an oriented function and process for obtaining same

ABSTRACT

Preparation of a slip including more than 4% and less than 50% of ceramic particles and including more than 1% of orientable ceramic particles made of a material including an oriented function, as volume percentage on the basis of the set of ceramic particles, wherein the fraction of non-orientable ceramic particles has a median length less than ten times the median length of the orientable ceramic particles if the set of ceramic particles includes less than 80%, as volume percentage, of orientable ceramic particles, oriented freezing of the slip by movement of a solidification front at a speed less than the speed of encapsulation of the ceramic particles; elimination of the crystals of solidified liquid phase of said block, optionally, sintering.

FIELD OF TECHNOLOGY

The invention relates to a process for manufacturing a product,optionally sintered, obtained by oriented freezing of a slip, thenremoval of the crystals obtained by said freezing. The invention alsorelates to a product with truncated tubular pores.

PRIOR ART

A product, optionally sintered, obtained by oriented freezing of a slip,then removal of the crystals obtained by said freezing, is usedconventionally in numerous applications, and in particular in a fuelcell, as catalyst support, or in a heat exchanger.

US 2007/0249493 describes a product obtained by oriented freezing of asilica gel. A silica sol is first prepared, which sol is composed of asodium silicate solution exhibiting a concentration of SiO₂ molecules of1.9 mol/l. Carbon nanofibres are dispersed in this silica sol which issubsequently gelled so as to obtain said silica gel, which issubstantially a solid.

The paper “Platelets self-assemble into porous nacre during freezecasting”, Ph. Hunger et al., Journal of the Mechanical Behaviour ofBiomedical Materials, Vol. 19, pages 87-93, 2012, describes a processfor the oriented freezing of a synthetic nacre from a slip comprisingalumina particles of platelet or spherical form. In addition, this paperdescribes the mechanical properties (modulus of elasticity, toughness,breaking strength) of the product obtained.

The paper “Fabrication of porous PZT-PZN piezoelectric ceramics withhigh hydrostatic figure of merits using camphene based freeze casting”,S-H. Lee et al., Journal of the American Ceramic Society, Vol. 90, No.9, 2007, describes a porous product obtained by oriented freezing of aslip comprising suspended particles of any shape, which are obtained bygrinding spherical agglomerates.

There exists a constant need for a product suited to these applicationsand exhibiting properties whose intensity is variable in the directionunder consideration.

One aim of the invention is to satisfy this need, at least partially.

SUMMARY OF THE INVENTION

The invention relates to a process for manufacturing a product,optionally sintered, said process comprising the following steps:

-   -   a) preparing a slip comprising an ensemble of ceramic particles        in suspension in a liquid phase, the ensemble of ceramic        particles representing more than 4% and less than 50% of the        volume of the slip and comprising, in percentage by volume based        on the ensemble of ceramic particles, more than 1% of orientable        ceramic particles of a material with oriented function, the        fraction of the nonorientable ceramic particles having a median        length ten times less than the median length of the orientable        ceramic particles L₅₀ if the ensemble of ceramic particles        comprises less than 80%, in percentage by volume, of orientable        ceramic particles,    -   b) optionally, pouring the slip into a mould and/or removing air        bubbles contained in the slip,    -   c) oriented freezing of the slip by displacement of a        solidification front so as to form a block of frozen slip, the        velocity Vp of the solidification front being less than the        velocity of encapsulation of the ceramic particles Vc and        adjusted so as to form crystals of solidified liquid phase        separated by walls with an average thickness “e” greater than or        equal to the average thickness of the orientable ceramic        particles W1 ₅₀;    -   d) optionally, removing said block from the mould,    -   e) removing the crystals of solidified liquid phase from said        block, optionally removed from the mould, preferably by        sublimation, so as to obtain a macroporous preform,    -   f) optionally, removal of binder from the macroporous preform        obtained at the end of step e),    -   g) optionally, sintering the macroporous preform so as to obtain        a sintered product, this step g) being obligatory if, in step        a), the amount of orientable ceramic particles of a material        with oriented function is less than 80%, in percentage by volume        based on the ensemble of the ceramic particles;    -   h) optionally, machining and/or impregnation of said sintered        product.

The ceramic particles may be replaced, partially or completely, withequivalent amounts of precursors that are transformed into ceramicparticles so as to obtain said ensemble of ceramic particles before stepc), and/or

may be replaced, partially or completely, with equivalent amounts ofparticles of the same form of a ceramic precursor that is transformedinto ceramic in step f) or g).

As will be seen in more detail in the rest of the description, theinventors discovered that a process according to the invention makes itpossible to manufacture a macroporous preform in which the walls of themacropores comprise, on at least a portion of their thickness, a stack,oriented overall, of orientable ceramic particles. Remarkably, thepresence of the orientable particles of a material with orientedfunction makes it possible to benefit from the resulting orientation ofthe oriented freezing in order to obtain a product exhibiting propertieswhose intensity is highly variable in the direction under consideration.

More particularly, the use of orientable ceramic particles of a materialwith oriented function makes it possible to obtain a product having, fora given property, an amplified intensity along at least one direction,in comparison with the use of orientable ceramic particles made of amaterial not having such an oriented function. In particular, such acomparison can be carried out by considering a material with orientedfunction, said property of which has an average intensity (along threedirections of the space forming an orthogonal marker), substantiallyequal to the intensity of the property of a material not having anoriented property.

Without being bound to this theory, the inventors explain the particularstructure of a product according to the invention on the basis that, asthe velocity Vp of displacement of the solidification front is less thanthe velocity of encapsulation of the ceramic particles, thesolidification front pushes back the orientable particles. During theirdisplacement, these orientable ceramic particles become oriented and canthus form a stack roughly following the direction of displacement of thesolidification front.

In one preferred embodiment, the form of the orientable particles isselected in relation to the orientation of the function, so that theoriented freezing makes it possible to obtain properties whose intensityis variable in a chosen direction.

More particularly, a particular arrangement of such orientableparticles, for example in the form of a stack, makes it possible toincrease the response of a property when this arrangement is correlatedwith the orientation of the function in said particles. The response maythus be increased, in a preferred plane or direction, as a function ofthe number of particles having roughly the same orientation.

The oriented function may notably correspond to thermal, electrical,piezoelectric or magnetic properties. Hexagonal boron nitride, graphite,graphene, for example, are ceramic materials whose thermal conductivityis oriented. Hexagonal graphite, graphene, are examples of ceramicmaterials whose electrical conductivity is oriented. PMN PT, or(1−x)[Pb(Mg_(1/3)Nb_(2/3))O₃]-x[PbTiO₃], with x between 0 and 1, PbTiO₃,(Li,Na,K)(Nb,Ta,Sb)O₃, in particular potassium sodium niobate, areexamples of piezoelectric materials. Haematite is an example of ceramicmaterial whose ferromagnetic properties are oriented.

In one embodiment, the ensemble of the ceramic particles comprises:

-   -   a first particulate fraction consisting of orientable,        preferably anisotropic, particles, of a material with oriented        function, having a median length L′₅₀ and representing more than        1% of the ceramic particles, in percentage by volume based on        the ensemble of the ceramic particles; and    -   a second particulate fraction having a median length D₅₀ at        least ten times less than L′₅₀ (i.e. D₅₀<L′₅₀/10) and        representing more than 5% of the ceramic particles, in        percentage by volume based on the ensemble of the ceramic        particles;        the first and second particulate fractions together representing        more than 80% of the ensemble of the ceramic particles, as        percentage by volume.

During the displacement and orientation of the orientable particles, theparticles of the second particulate fraction are progressively trappedin the spaces between the orientable particles. This results in aparticularly high apparent density, and therefore superior mechanicalproperties, notably after sintering.

Moreover, especially when the amount of anisotropic ceramic particles islarge enough, the inventors found that the particles of the secondparticulate fraction may, during sintering, coalesce with theneighbouring anisotropic particles to form anisotropic particles oflarger size. This results in a surprising stack of anisotropicparticles, corresponding to a remarkable apparent density. The sinteringstep g) is therefore preferred.

A process according to the invention may further comprise one or more ofthe following optional features, which may be combined in all possiblecombinations:

-   -   The material with oriented function is selected from the group        formed by hexagonal boron nitride, graphite, graphene, PMN PT,        or (1−x)[Pb(Mg_(1/3)Nb_(2/3))O₃]-x[PbTiO₃], with x between 0 and        1, PbTiO₃, (Li,Na,K)(Nb,Ta,Sb)O₃, in particular potassium sodium        niobiate, and haematite.    -   A direction is determined and then the form of the orientable        particles is selected in relation to the orientation of the        function, so that the oriented freezing makes it possible to        obtain properties whose intensity is variable in said direction.    -   The ensemble of ceramic particles comprises, in percentage by        volume based on the ensemble of the ceramic particles,        -   a first particulate fraction consisting of orientable,            preferably anisotropic, particles, of a material with            oriented function, having a median length L′₅₀ and            representing more than 1% of the ceramic particles, in            percentage by volume based on the ensemble of the ceramic            particles; and        -   a second particulate fraction having a median length D₅₀ at            least ten times less than L′₅₀ and representing more than 5%            of the ceramic particles, in percentage by volume based on            the ensemble of the ceramic particles;            the first and second particulate fractions together            representing more than 80% of the ensemble of the ceramic            particles, as percentage by volume.    -   The first particulate fraction represents more than 5% and less        than 15% of the volume of the ceramic particles, and the        particles of the first particulate fraction are of a material        with oriented function, and the first and second particulate        fractions together represent more than 95% of the volume of the        ensemble of ceramic particles, and the granulometric        distribution of the ceramic particles is bimodal, the two        principal modes corresponding to the first and second        particulate fractions, respectively, the process preferably        comprising a sintering step g).    -   The first particulate fraction represents more than 90% of the        volume of the ceramic particles, and the particles of the first        particulate fraction are of a material with oriented function,        and the first and second particulate fractions together        represent more than 95% of the volume of the ensemble of ceramic        particles, and the granulometric distribution of the ceramic        particles is bimodal, the two principal modes corresponding to        the first and second particulate fractions, respectively, the        process comprising a sintering step g).    -   The oriented function corresponds to a thermal, electrical,        piezoelectric or magnetic property.    -   The orientable ceramic particles are boron nitride platelets,        each platelet having a thermal conductivity in the main plane of        the platelet greater than the thermal conductivity along the        thickness of the platelet.    -   The orientable ceramic particles are anisotropic particles or        multifaceted particles having more than two facets.    -   More than 50% of the orientable particles belong to one and the        same shape class, in percentage by volume.    -   The ensemble of ceramic particles comprises, in percentage by        volume based on the ensemble of the ceramic particles, more than        80% of orientable ceramic particles.    -   The material constituting the orientable, or anisotropic,        ceramic particles and/or the ceramic particles of the second        particulate fraction and/or the particles of the fraction        complementary to the orientable particles or to the anisotropic        particles is selected from oxides, nitrides, carbides,        carboxynitrides and mixtures thereof.    -   Said material is selected from the group comprising zirconium        oxide or zirconia (ZrO₂), partially stabilized zirconium oxide,        stabilized zirconium oxide, yttrium oxide (Y₂O₃), doped yttrium        oxide, preferably yttrium oxide doped with samarium oxide,        titanium dioxide (TiO₂), aluminosilicates such as mullite,        cordierite (Al₃Mg₂AlSi₅O₁₈), aluminium oxide or alumina (Al₂O₃),        hydrated aluminas, and in particular boehmite, magnesium oxide        (MgO), talc (Mg₃Si₄O₁₀(OH)₂), nickel oxide (NiO), the iron        oxides (FeO, Fe₂O₃, Fe₃O₄), cerium oxide, doped cerium oxide,        the oxides with perovskite structure, in particular the        gallates, compounds comprising lanthanum of the type LaAlO₃ or        LaGaO₃ or La_((1−x))Sr_(x)MO₃, with 0≤x≤1 and M an element        selected from the group comprising chromium, cobalt, magnesium,        iron, gadolinium, manganese and mixtures thereof; the oxides        with perovskite structure doped with platinum and/or palladium        and/or rhodium and/or gold and/or silver, for example        La_((1−x))Sr_(x)M_((1−y))M′_(y)O₃ with 0≤x≤1, 0≤y≤0.15, M being        an element selected from the group comprising chromium, cobalt,        magnesium, iron, gadolinium, manganese and mixtures thereof, M′        being an element selected from the group comprising platinum,        palladium, rhodium, gold, silver and mixtures thereof, the        compounds comprising titanium of the type        La₄Sr₈Ti₁₁Mn_(1−x)Ga_(x)O₃₈ with 0≤x≤1 and        La₄Sr₈Ti_(12-n)Mn_(n)O₃₈ with 0≤n≤1, the compounds of the type        BaTiO₃, BaZrO₃, Pb(Mg_(0.25)Nb_(0.75))O₃,        Ba(Zn_(0.25)Nb_(0.75))O₃, Pb(Zn_(0.25)Nb_(0.75))O₃, PbTiO₃,        CaCu₃Ti₄O₁₂, the compounds with a structure of the bimevox type,        for example Bi₂V_(1−x)Me_(x)O_(z) with 0≤x≤1, z such as to        ensure electroneutrality, and Me an element selected from the        group comprising magnesium, aluminium, silicon, titanium,        cobalt, nickel, copper, zinc, manganese, antimony, tantalum,        niobium, chromium, molybdenum, tungsten, uranium and mixtures        thereof, the compounds with a structure of the lamox type, for        example La₂Mo₂O₉, the compounds with apatite structure, for        example Me′₁₀(XO₄)₆Y′₂ in which Me′ is a metal cation selected        from the group comprising Ca²⁺, Cd²⁺, Sr⁺, Ba²⁺, Pb²⁺, Na⁺, K⁺,        cations of rare earths, preferably La³⁺ and Nd³⁺, Al³⁺, U⁴⁺,        Th⁴⁺, (XO₄) is an anionic group selected from PO₄ ³⁻, SiO₄ ⁴⁻,        AsO₄ ³⁻, MnO₄ ⁻, SO₄ ²⁻, CO₃ ²⁻, HPO₄ ²⁻, SiO₄ ⁴⁻, GeO₄ ⁴⁻ and        mixtures thereof; and Y′ is an anion selected from F⁻, Cl⁻, OH⁻,        Br⁻, I⁻, CO₃ ²⁻, O²⁻ and mixtures thereof, the compounds of type        SrCe_(1−x)M_(x)O₃ with 0≤x≤1 and M a rare earth, M preferably        being ytterbium, the compounds of the type BaCe_(1−x)M_(x)O₃,        with 0≤x≤1 and M a rare earth, for example the compound BaCeO₃,        the compounds of the family La_(x)Sr_(1−x)ScO₃ with 0≤x≤1, for        example La_(0.9)Sr_(0.1)ScO₃, the zeolites of structure        Na_(x1)Ca_(x2)Mg_(x3)Ba_(x4)K_(x5)Al_(x6)(Si_(x7)O_(x8)),x9H₂O,        x1 to x9 being positive integers or zero fulfilling the        following conditions: x6>0, x7>0, x8>0, x9>0 and        x1+x2+x3+x4+x5>0, KNbO₃ optionally doped preferably with lithium        and/or tantalum and/or barium, NaNbO₃ optionally doped        preferably with lithium and/or tantalum and/or barium,        (K_(0.5)Na_(0.5))NbO₃ optionally doped preferably with lithium        and/or tantalum and/or barium, aluminium nitride, boron nitride,        silicon nitride, titanium nitride, titanium carbide, silicon        carbide, tungsten carbide, zirconium carbide and mixtures        thereof.

The invention also relates to a preform obtained or that can have beenobtained at the end of a process comprising steps a) to e) above.

The invention also relates to a product obtained or that can have beenobtained by a process according to the invention.

The present invention also relates to a product, optionally sintered,comprising a plurality of macroscopic truncated tubular pores extendingroughly parallel to one another in a longitudinal direction, eachtruncated tubular pore being delimited by a wall,

the walls between said truncated tubular pores comprising more than 5%,in percentage by volume, of orientable ceramic grains of a material withoriented function.

As will become clear in the rest of the description, a process accordingto the invention leads to orientation of the orientable ceramicparticles during product manufacture, that is to say that the orientablegrains of the product, corresponding to the orientable particles of theslip, are oriented.

Preferably, a product according to the invention further comprises one,and preferably several, of the following optional features:

-   -   The product comprises a plurality of macroscopic truncated        tubular pores extending roughly parallel to one another in a        longitudinal direction, each truncated tubular pore being        delimited by a wall, the walls between said truncated tubular        pores comprising more than 5%, in percentage by volume, of        orientable ceramic grains having an oriented function.    -   Said function is oriented in the direction of the truncated        tubular pores.    -   The wall comprises a peripheral stratum consisting of one or        more layers of orientable ceramic grains.    -   The dispersion of the orientation of the grain boundaries is        below 30°, preferably below 15°.

The invention further relates to a device selected from a ceramicelectrochemical cell, a fuel cell, and in particular an SOFC cell, anIT-SOFC cell, a PCFC cell, an element for filtration of a liquid orgaseous fluid, a microstructure for storage used for storing a substancein the macropores, a catalyst support, a heat exchanger, a heatinsulator, a fluid distributor allowing said fluid to be transported,and notably a gas distributor, a separator of drops or a trickling unitfor an air conditioning system, a battery, and notably an electrolyte ofa battery, a supercapacitor, a humidity adsorber, a micro-combustionchamber, a transducer, a movement sensor, an ultrasonography probe, abaking support, a sintering muffle, in particular a muffle used forsintering aluminium nitride (AlN), said device comprising a productaccording to the invention or manufactured by a process according to theinvention. This product may in particular be used as impregnatedelectrolyte in the aforementioned cells.

In an additional development, the invention relates to a dense product,optionally sintered, obtained by a process according to the inventionfurther comprising, after step d), a step e′) of compression, preferablyfollowing step e), consisting of compressing said block in a directionroughly parallel to the direction of the thickness of the crystals ofsolidified liquid phase, so as to obtain a dense product according tothe invention.

A dense product according to the invention may notably have a relativedensity above 85%, comprising in percentage by volume more than 50% oforientable ceramic grains, and comprising more than 5%, in percentage byvolume, of orientable ceramic grains, preferably rodlets or platelets,and having an oriented function, more than 80% of the orientable ceramicgrains being roughly parallel to one another.

Preferably, the thickness of the dense product is above 50 μm,preferably above 100 μm, preferably above 500 μm, or even above 1 mm, oreven above 5 mm, or even above 1 cm, or even above 5 cm.

Advantageously, a dense product according to the invention has anoptimum response of the oriented function per unit of product volume,and also good mechanical properties, notably breaking stress andtoughness, especially in comparison with the porous product obtained atthe end of step e), f) or g) of a process not comprising step e′).

DEFINITIONS

-   -   “Ceramic material” means any nonmetallic and inorganic material.    -   “Velocity of encapsulation of the ceramic particles”, Vc, means        the velocity of the solidification front, beyond which, during        passage of said solidification front, the ceramic particles are        no longer pushed back by the solidification front between the        crystals of solidified liquid phase, but remain trapped in these        crystals of solidified liquid phase.        -   The velocity of encapsulation of the ceramic particles of a            slip depends notably on the amount of particles in            suspension in the slip, their size, as well as the viscosity            of said slip. There is a simple test for determining this            velocity of encapsulation.        -   The velocity of encapsulation is described for example in            “The encapsulation of particles and bubbles by an advancing            solidification front”, Park et al., Journal of Fluid            Mechanics, 2006, Vol. 560, pp. 415-436. In particular, FIG.            9 of this publication summarizes the influence of particle            size on the velocity of encapsulation.    -   “Oriented” freezing means freezing carried out progressively in        a defined direction.    -   “Sublimation” is an operation, generally under vacuum, that        consists of evaporating solidified liquid phase without melting        it.    -   “Melting” is an operation that consists of melting solidified        liquid phase.    -   “Temporary” means “removed from the product during removal of        binder or sintering”.    -   The median cross-section of a particle or of a pore is the        section in a transverse plane, i.e. perpendicular to the        direction of the length (or “longitudinal direction”) of the        particle or pore, which extends to mid-length of said particle        or said pore. For clarity, the lengths of the particles of the        first and second particulate fractions have been referenced L        and D, respectively.    -   “Flattened” describes a pore whose width is more than 5 times,        preferably more than 10 times, or even more than 20 times        greater than its thickness, the width and thickness being        measured in a median cross-section of the pore.    -   “Particles” are the solid elements constituting a powder or in        suspension in a slip. In a sol, the dissolved matter therefore        does not constitute a particle. The structure of a gel, obtained        by gelling of a sol, comprises hardly any particles. After        forming and in the interests of clarity, the particles of the        slip are called “grains”. The dimensional characteristics        relating to a grain are those of the corresponding particle. In        particular, a grain is regarded as “anisotropic” when it        corresponds to an anisotropic particle.        -   A particle is “orientable” when it is oriented in a            particular way under the effect of passage of the            solidification front. An orientable shape, for example of            platelet or rodlet or rice grain, or a multifaceted shape            (with number of faces above 2 and below 35) makes an            orientable particle. When a multifaceted particle only has            two faces, tests have shown that it must be anisotropic to            be orientable. There is a simple test for verifying whether            a particle is orientable.        -   A particle (or a grain) is considered to be “multifaceted”            when it has at least 2 facets, a facet being a surface            delimited by an edge. A “nut” shape is an example of a shape            with two facets.        -   A multifaceted particle (or grain) may in particular be            “polyhedral”, i.e. delimited on all sides by plane polygons.            A multifaceted particle (or grain) may in particular be            “regular” polyhedral if all its faces are regular polygons            of the same type and if all its vertices are of the same            degree. A regular polyhedron has a sphere tangential to each            face at its centre. A “cube” is a regular polyhedron            comprising 6 square faces.    -   “Direction of orientation of an orientable particle” is the        direction in which the orientable particle is oriented under the        effect of passage of the solidification front.    -   A “shape class” is a fraction that unites the orientable        particles having a specified shape, for example which unites all        the particles having a platelet shape (regardless of the        dimensions of these platelets).    -   A particle is regarded as “anisotropic” when the elongation        factor R between its length L and its thickness W1, i.e. R=L/W1,        is greater than 4.    -   The “length” L of a particle is its largest dimension observable        on a photograph taken in a direction perpendicular to the plane        on which said particle rests.        -   The “width” W2 and the “thickness” W1 of a particle are the            lengths of the major and minor axes, respectively, of the            smallest possible ellipse in which the median cross-section            of said particle can be inscribed.        -   A particle has a “rodlet” shape when it meets the following            three conditions:            -   1) 4≤L/W≤10 and W=(W1+W2)/2,            -   2) 4≤L/W1, and            -   3) W2<1.5*W1.        -   FIG. 1 shows a schematic diagram of a particle with a rodlet            shape.        -   A particle has a “platelet” shape when it meets the            following two conditions:            -   1) 4≤L/W, and            -   2) W2≥1.5W1, preferably W2≥2W1.        -   Preferably, the cross-section of a platelet is roughly            constant over the whole length of the platelet, is roughly            polygonal and has at least 4 sides.        -   FIG. 2 shows a schematic diagram of a particle of platelet            shape.        -   Particles in the form of platelets or rodlets therefore            differ appreciably from spherical or fibrous shapes, wires,            filaments, needles or cubes.    -   The “median” value of a property of the particles of an ensemble        of particles is the value of this property that divides the        particles of said ensemble into first and second populations        that are equal in number, these first and second populations        only comprising particles having a value of said property        greater than or equal to, or less than respectively, the median        value. For example, the median length of an ensemble of        particles is the length dividing the particles into first and        second populations equal in number, these first and second        populations only comprising particles having a length greater        than or equal to, or less than respectively, the median length.    -   “Tubular pore” means a pore that has the general shape of a tube        opening at one of its two ends (“blind pore”) or at both ends        (“through-pore”). In a product according to the invention, the        direction of a truncated tubular pore is qualified as        “longitudinal direction” and is a function of the direction of        advance of the solidification front.    -   A truncated tubular pore is called “macroscopic”, or is called a        “macropore” if it has a median cross-section having an        equivalent diameter above 0.15 μm and below 450 μm.        -   For an ensemble of parallel truncated tubular pores, the            average median transverse plane is the plane perpendicular            to the direction of the truncated tubular pores and passing,            on average for all the pores, at mid-length of said            truncated tubular pores, mid-length being defined on average            for all the truncated tubular pores.        -   “Cross-section” of a truncated tubular pore is the section            of this pore in a transverse cutting plane. The length of a            truncated tubular pore is the dimension measured along its            axis, between its two ends.        -   The “tubular” character of a pore can be determined by            observation of photographs of the pores, in particular in            perspective or in longitudinal section.    -   The “equivalent diameter” or “size” of the opening or of a        section of a pore is the diameter of a disk of the same area as        said opening or said section.    -   The convexity index Ic of a pore in a transverse cutting plane        is the ratio Sp/Sc where Sp denotes the area of the        cross-section of the pore, delimited by its perimeter, and Sc        denotes the convex surface of this cross-section, i.e. the        surface of the convex envelope of this cross-section.        -   Conventionally, “convex envelope” is the line of closed            shape convex outwards, of minimum length and containing the            perimeter of said pore, the perimeter denoting            conventionally the shape line that closes the pore section.            The convex envelope is therefore superposed on the convex or            rectilinear portions of the perimeter and follows the chords            joining in each case two convex or rectilinear portions            separated by a concave portion (viewed from outside). A            convex envelope may be compared to the region that would be            delimited by a stretched elastic band resting exclusively on            the perimeter.        -   For example, FIG. 10 shows the perimeter 10 of a            cross-section of a pore, as well as the convex envelope 12            of this pore. With S_(p) denoting the surface of the pore,            delimited by the perimeter 10, and S_(c) the convex surface            of said pore corresponding to the surface delimited by the            convex envelope 12, then the convexity index Ic is equal to            S_(p)/S_(c). The convexity index Ic is therefore equal to            100% for a circle, an ellipse or an oval, but also for a            polygon such as a triangle, a parallelogram, a hexagon, a            pentagon. It is less than 100% for the pores, whose            perimeter, viewed from outside, has one or more recesses.        -   FIG. 11 shows a pore whose perimeter has concave portions 16            ₁₋₄ and convex portions 14 ₁₋₄. In this figure, the convex            envelope 12 joins the two convex portions 14 ₁ and 14 ₃. The            convex portions (14 ₁₋₂) are ignored.        -   The convexity index Ic may be evaluated with the following,            non-limiting method:        -   The sample to be analysed is infiltrated with a resin, for            example an epoxy resin. A slice to be analysed is cut            perpendicularly to the direction of solidification, and then            polished in order to obtain a good surface condition, said            polishing being carried out at least with a paper grade            1200, preferably with a diamond paste. Images are then            obtained using a scanning electron microscope (SEM),            preferably in a mode using backscattered electrons (BSE            mode) in order to obtain very good contrast between the            ceramic phase and the resin. Each image has at least            1280×960 pixels, excluding the scale bar. The magnification            used is such that the width of the image is between 50 times            and 100 times the average pore size. A first image may be            recorded based on a visual estimate of the average pore            size.        -   The image is then analysed using the imageJ software,            available on the website http://rsbweb.nih.gov/ij/ by the            following method:            -   open the image in imageJ;            -   crop the image (“Crop” function) to remove the scale bar                or any other supplementary information present on the                image;            -   adjust the brightness with the function                “Image>Adjust>Brightness/contrast”, then click on                “Auto”;            -   digitize the image with the Multithresholder function                (“Plugin>Filter>Multithresholder”), then select the                “Isodata” mode to fix the threshold making it possible                to distinguish the material to be analysed from the                infiltrated resin;            -   ensure that the pores to be analysed appear properly in                black on the image (value 255 for white, 0 for black).                If otherwise, invert the image using the “Edit>Invert”                function;            -   analyse the pores using the “Analyse>Analyse particles”                function. The possible parameters for analysis of the                pores are as follows: “size min”: 0.2×average size of                pores measured previously; “size max”: none, “exclude on                edges” so as not to analyse the pores intercepted by the                edges of the image, do not tick the option “include                holes”;            -   check that at least 50 pores have been analysed. If                otherwise, analyse other images in such a way that the                total number of pores analysed is greater than or equal                to 50;            -   in the table of results, for each pore, record the                solidity index (“solidity”);            -   classify the pores by increasing solidity index;            -   plot the cumulative fraction by number as a function of                the solidity index Is.        -   The solidity index measured in this way gives a very good            approximation of the average convexity index Ic.    -   “Fully stabilized zirconium oxide” means a zirconium oxide        having an amount of zirconium oxide in a monoclinic        crystallographic form below 1 wt %, the complement consisting of        zirconium oxide in a quadratic crystallographic form, stable        and/or metastable, and/or cubic.    -   A material is said to have “oriented function” when it has at        least one property, other than mechanical, that is “oriented”,        i.e. whose intensity is variable depending on the orientation of        measurement, in a proportion such that there is at least one        direction in which said property is at least 1.1 times higher        than the average value of said property in the other directions.        Such a property may be for example an electrical, thermal,        dielectric, magnetic or else optical property. Thus, a particle        in a material with oriented function has at least one property        whose intensity is a function of the direction in which        measurement of the property is carried out. Alumina and silica        are not materials with oriented function, in contrast to boron        nitride, whose thermal diffusivity is a function of the        direction in which it is measured.    -   “Direction of function” means a direction in which the        characteristic function of a material with oriented function        displays an intensity extremum.    -   By definition, a “bimodal” distribution shows up two categories        that are not contiguous having the highest values, called “main        peaks” or “principal modes”.    -   Unless stated otherwise, a mean value is an arithmetic mean.    -   Unless stated otherwise, all the percentages relating to the        composition of a slip according to the invention are percentages        by volume relative to the volume of the slip.    -   The percentages by volume of an ensemble of particles correspond        to percentages considering the sum of the volumes of each of the        particles considered. The sum of these volumes is calculated        conventionally by the ratio of the mass of said ensemble of        particles divided by the absolute density of the material of        said particles. For example, if the second particulate fraction        represents less than 20% “of the volume of the ensemble of        ceramic particles”, or in an equivalent manner “of the volume of        the ceramic particles” or “in percentage by volume based on the        ensemble of ceramic particles” or “in percentage by volume based        on the ceramic particles”, the volumes to be compared are the        volume of the particles of the powder constituting the second        particulate fraction and the volume of the ensemble of ceramic        particles.    -   The “relative density of a product” corresponds to the ratio        equal to apparent density of the product divided by the absolute        density of the product, expressed as a percentage.    -   “Apparent density of a product” means, in the sense of the        present invention, the ratio equal to the mass of the product        divided by the volume occupied by said product. It can be        measured by imbibition, according to the principle of        hydrostatic buoyancy.    -   “Absolute density of a product” means, in the sense of the        present invention, the ratio equal to the mass of dry matter of        said product after grinding to a fineness such that hardly any        closed porosity remains, divided by the volume of said mass of        dry matter after grinding. It may be measured with a helium        pycnometer.    -   The various characteristics of a product according to the        invention may be determined by the methods of characterization        used for the examples given below.

BRIEF DESCRIPTION OF THE FIGURES

Other features and advantages of the invention will become clearer onexamining the drawings, supplied for purposes of illustration andnon-limiting, in which:

FIGS. 1 and 2 show schematically a rodlet and a platelet, respectively;

FIG. 3 shows schematically a cross-section of a wall of a truncatedtubular pore of a product according to the invention;

FIGS. 4, 5, 6, 7, 8 a, 8 b, 9 show images taken with a scanning electronmicroscope (SEM) of the products of examples 1, 2, 1, 2, 4 beforesintering, 4 after sintering, and 8, respectively;

FIGS. 10 and 11 illustrate the method for evaluating the convexityindex;

FIGS. 12 to 28 show a cube, a saw-tooth fibre, prismatic chains, apseudo-cubo-octahedron, square cylinders, tetrapods, pointed tetrapods,an octapod, a truncated cube, a cubo-octahedron, a truncated octahedron,an octahedron, stars, a pillar, an icosahedron, hexagonal bipyramids,microtubes, respectively;

FIG. 29 shows the curve of mercury porosity measurement carried out onthe product of example 5; and

FIG. 30, 31 respectively, shows a product comprising flattened poresafter step e), and a dense product obtained by compression in step e′)of the product shown in FIG. 30 respectively.

In the figures, identical references have been used to denote identicalor similar objects.

DETAILED DESCRIPTION

Process According to the Invention

A product according to the invention may be manufactured by a processcomprising steps a) to h) given above.

In step a) of preparing the slip, a suspension of a powder of ceramicparticles is prepared.

The amount of particles in suspension is preferably above 8% and/orbelow 40%, preferably below 25%, in percentage by volume of the slip.The ceramic particles preferably represent more than 90%, preferablymore than 95%, or even more than 99%, or even roughly 100% of the volumeof the particles in suspension.

In one embodiment, the slip comprises silica, which is preferably tomore than 50%, preferably to more than 60%, preferably to more than 70%,preferably to more than 80%, preferably to more than 90%, preferably tomore than 95%, preferably to more than 99%, or even roughly completelyin the form of particles, in percentages by weight based on the totalweight of silica.

The ensemble of ceramic particles preferably comprises:

-   -   a first particulate fraction consisting of orientable,        preferably anisotropic, particles having a median length L′₅₀        and representing more than 1% of the ceramic particles, in        percentage by volume based on the ensemble of ceramic particles;        and    -   a second particulate fraction having a median length D₅₀ at        least ten times less than L′₅₀ (i.e. D₅₀<L′₅₀/10) and        representing more than 5% of the ceramic particles, in        percentage by volume based on the ensemble of ceramic particles.

The first particulate fraction consists of orientable, preferablyanisotropic, particles, but does not necessarily comprise all theorientable, or anisotropic, particles of the ensemble of ceramicparticles.

The first particulate fraction consists of orientable, preferablyanisotropic, particles but does not necessarily represent all theorientable, or anisotropic, particles, respectively, of the ensemble ofceramic particles. According to the invention, there must be at leastone such first particulate fraction, but there may be several of them. Afirst particulate fraction must nevertheless represent more than 1% ofthe ensemble of ceramic particles.

Moreover, the second particulate fraction consists of any particles,which, together, must have a median length D₅₀ at least ten times lessthan L′₅₀. According to the invention, there must be at least one suchsecond particulate fraction, but there may be several of them. A secondparticulate fraction must nevertheless represent more than 5% of theensemble of ceramic particles.

The first particulate fraction preferably represents more than 2%,preferably more than 3%, preferably more than 5%, by volume of theceramic particles, or even of the orientable ceramic particles, or evenof the anisotropic ceramic particles. The proportion of the firstparticulate fraction is not, however, limited to these ranges and thisproportion may be above 10%, above 20%, above 30%, above 40%, above 50%,above 60%, above 70%, above 80%, or above 90%, or even 100% by volume ofthe ceramic particles, or of the orientable ceramic particles, or of theanisotropic ceramic particles.

The second particulate fraction has a median length D₅₀ preferably atleast fifteen times less than L′₅₀, preferably at least twenty timesless than L′₅₀, preferably at least thirty times less than L′₅₀,preferably at least fifty times less than L′₅₀.

The second particulate fraction may in particular be included in thefirst particulate fraction.

The proportion of the second particulate fraction may preferably beabove 7%, preferably above 10%, preferably above 15%, or even above 20%,above 30%, above 40%, above 50%, above 60%, above 70%, above 80%, above90%, above 95%, above 98%, in percentage by volume of the ceramicparticles, or even of the orientable ceramic particles, or even of theanisotropic ceramic particles.

The proportion of the second particulate fraction may be above 7%, above10%, preferably above 15%, or even above 20%, above 30%, above 40%,above 50%, above 60%, above 70%, above 80%, above 90%, above 95%, above98%, in percentage by volume of the non-anisotropic ceramic particles.

In one embodiment, the first and second particulate fractions aredetermined so that together they represent more than 90%, more than 95%,or even 100% of the ensemble of ceramic particles, in percentage byvolume. The complement to 100% preferably consists of ceramic particleshaving a median length less than, preferably 2 times less than, 5 timesless than the median length L′₅₀ of the first particulate fraction.

In one embodiment, the first particulate fraction unites the ensemble oforientable or anisotropic particles, and the second particulate fractionunites the ensemble of particles having a length D at least five times,preferably at least ten times, or even at least fifteen times less thanL′₅₀.

In one embodiment, the first particulate fraction unites the ensemble oforientable or anisotropic particles, and the second particulate fractiononly comprises particles that are not orientable, or even notanisotropic. Preferably, the median length D₅₀ is at least twelve timesless than L′₅₀, preferably at least fifteen times less than L′₅₀,preferably at least twenty times less than L′₅₀, preferably at leastthirty times less than L′₅₀, preferably at least fifty times less thanL′₅₀.

In one embodiment,

-   -   the first particulate fraction consisting of orientable,        preferably anisotropic, particles represents more than 50%,        preferably more than 60%, preferably more than 70%, preferably        more than 80%, or even more than 90%, by volume of the ceramic        particles, and    -   the second particulate fraction preferably represents more than        7%, preferably more than 10%, preferably more than 15%, by        volume of ceramic particles, and    -   more than 90%, more than 95%, or even roughly 100% by volume of        the particles of the second particulate fraction are preferably        not anisotropic, or even not orientable, and    -   the first and second particulate fractions together represent        preferably more than 90%, preferably more than 95%, or even 100%        of the volume of the ensemble of ceramic particles, and    -   the granulometric distribution of the ceramic particles is        bimodal, the two modes being centred on the lengths D_(a) and        D_(b), D_(a) preferably being less than D_(b)/10, D_(b) and        D_(a) preferably being centred on the lengths L′₅₀ and D₅₀,        respectively.

In this embodiment, the process preferably comprises a sintering stepg).

In one embodiment,

-   -   the first particulate fraction consisting of orientable,        preferably anisotropic, particles represents less than 50%,        preferably less than 30%, preferably less than 15% and more than        5%, by volume of the ceramic particles, and    -   the first particulate fraction has an average elongation factor,        Rm, preferably greater than 10, or even greater than 15, and    -   more than 90%, more than 95%, or even roughly 100% by volume of        the particles of the second particulate fraction are preferably        not anisotropic, or even not orientable, and    -   the first and second particulate fractions together represent        preferably more than 95%, or even 100% of the ensemble of        ceramic particles, and    -   the granulometric distribution of the ceramic particles is        bimodal, the two modes being centred on the lengths D_(a) and        D_(b), D_(a) preferably being less than D_(b)/10, D_(b) and        D_(a) preferably being centred on the lengths L′₅₀ and D₅₀,        respectively.

In this embodiment, the process preferably comprises a sintering stepg).

In one embodiment,

-   -   the first particulate fraction consisting of orientable,        preferably anisotropic, particles represents more than 80%,        preferably more 90%, even more than 95%, or even roughly 100% by        volume of the ceramic particles, and    -   the particles of the first particulate fraction are of a        material with oriented function, and    -   the second particulate fraction represents less than 20%,        preferably less than 15%, preferably less than 10%, preferably        less than 5%, of the volume of the ensemble of ceramic        particles, and    -   more than 90%, more than 95%, or even roughly 100% by volume of        the particles of the second particulate fraction are preferably        not anisotropic, or even not orientable, and    -   the first and second particulate fractions together represent        preferably more than 90%, preferably more than 95%, or even 100%        of the volume of the ensemble of ceramic particles, and    -   the granulometric distribution of the ceramic particles is        bimodal, the two modes being centred on the lengths D_(a) and        D_(b), D_(a) preferably being less than D_(b)/10, D_(b) and        D_(a) preferably being centred on the lengths L′₅₀ and D₅₀,        respectively.

In this embodiment, the process preferably comprises a sintering stepg).

In one embodiment,

-   -   the first particulate fraction consisting of orientable,        preferably anisotropic, particles represents less than 50%,        preferably less than 30%, preferably less than 15% and more than        5%, by volume of the ceramic particles, and    -   the particles of the first particulate fraction consisting of        orientable, preferably anisotropic, particles are of a material        with oriented function, and    -   more than 90%, more than 95%, or even roughly 100% by volume of        the particles of the second particulate fraction are preferably        not anisotropic, or even not orientable, and    -   the first and second particulate fractions together represent        preferably more than 95%, or even 100% of the volume of the        ensemble of ceramic particles, and    -   the granulometric distribution of the ceramic particles is        bimodal, the two modes being centred on the lengths D_(a) and        D_(b), D_(a) preferably being less than D_(b)/10, D_(b) and        D_(a) preferably being centred on the lengths L′₅₀ and D₅₀,        respectively.

In this embodiment, the process comprises a sintering step g).

Orientable Particles

In one embodiment, the amount of orientable, or even anisotropic,particles is below 50%, preferably below 30%, preferably below 15% basedon the volume of the ensemble of ceramic particles. Advantageously,transformation, during sintering, of the particles of the secondparticulate fraction that are not orientable or anisotropic, intoorientable or anisotropic particles, respectively, is promoted thereby.The shape of the latter may be similar to that of the surroundingorientable, or anisotropic, particles. As will be seen in more detail inthe rest of the description, this results in a remarkable increase inthe apparent density of the walls of the macropores and/or a remarkablechange in the properties, the intensity of which is variable as afunction of the direction considered when the orientable, preferablyanisotropic, particles formed after sintering are of a material withoriented function.

In one embodiment, the granulometric distribution of the ceramicparticles is bimodal, the two modes being centred on lengths D_(a) andD_(b), respectively, D_(a) preferably being less than D_(b)/10.

In a preferred embodiment, D_(b) is equal to L′₅₀ and D, is equal toD₅₀.

Preferably, the fraction of the non-anisotropic, or even non-orientable,ceramic particles has a median length less than ten times the medianlength of the anisotropic, or even orientable ceramic particlesrespectively, L₅₀, especially if the ensemble of ceramic particlescomprises less than 80%, in percentage by volume, of anisotropic, ororientable, ceramic particles respectively.

In one embodiment, the granulometric distribution of the orientable, oreven anisotropic, ceramic particles is bimodal, the two modes beingcentred on lengths L_(a) and L_(b), respectively, L_(a) preferably beingless than L_(b)/10. In one embodiment, L_(b) is equal to L′₅₀ and L_(a)is equal to D₅₀.

The median length of the orientable, preferably anisotropic, ceramicparticles or of the particles of the first particulate fraction, ispreferably above 0.1 μm, preferably above 0.2 μm, preferably above 0.3μm and/or below 50 μm, preferably below 25 μm, preferably below 10 μm,or even below 5 μm, or even below 1 μm.

The average thickness of the orientable, preferably anisotropic,particles or even of the particles of the first particulate fraction, W1₅₀ is preferably above 0.02 μm, preferably above 0.05 μm, preferablyabove 0.1 μm, preferably above 0.3 μm, preferably above 0.5 m and/orbelow 20 μm, preferably below 10 μm, preferably below 5 μm, preferablybelow 3 μm.

The average elongation factor of the ensemble of orientable, preferablyanisotropic, ceramic particles or even of the particles of the firstparticulate fraction, Rm (arithmetic mean of the elongation factors R,for the ensemble of orientable, or anisotropic, ceramic particlesrespectively) is preferably above 10, or even above 15 and/or ispreferably below 900, or even below 500, or even below 200.

In one embodiment, Rm≤15, especially when W2 ₅₀<1.5*W1 ₅₀.

In a preferred embodiment, more than 50%, more than 70%, more than 90%,more than 95%, or even roughly 100% by number of the orientable ceramicparticles, or even of the particles of the first particulate fraction,are platelets.

The orientable multifaceted particles of the ensemble of ceramicparticles, or even of the particles of the first particulate fraction,comprise preferably less than 30 facets, preferably less than 20 facets,preferably less than 15 facets, or even less than 10 facets, and/orpreferably more than 3 facets, preferably more than 4 facets.

The orientable multifaceted particles of the ensemble of ceramicparticles, or even of the particles of the first particulate fraction,are preferably selected from cubes, saw-tooth fibres, prismatic chains,pseudo-cubo-octahedra, square cylinders, tetrapods, pointed tetrapods,octapods, truncated cubes, cubo-octahedra, truncated octahedra,octahedra, pseudo-octahedra, stars, pillars, icosahedra, hexagonalcylinders, platelets, lenses, triangular platelets, microprisms,hexagonal bipyramids, microtubes, rodlets and mixtures thereof.

Preferably, in step a), more than 80%, preferably more than 90%,preferably more than 95% by number of the orientable, or evenanisotropic ceramic particles, or even of the particles of the firstparticulate fraction, may be classified in less than 5, preferably lessthan 4, preferably less than 3 shape classes, preferably one shapeclass, a shape class combining the ensemble of orientable particleshaving a specified shape.

Preferably, only one powder of orientable particles having the sameshape, for example a powder of particles in the form of platelets, isintroduced into the slip.

Conventionally, a shape class corresponds to one source of raw material,for example a powder of platelets of boron nitride. The preferredlimitation of the number of shape classes therefore signifies that theshape of the orientable, or even anisotropic particles, is not random,most of these particles having a shape selected from a “catalogue” ofshapes limited to 5 shapes at most.

In one embodiment, more than 50%, more than 60%, more than 70%, morethan 80%, more than 90%, or even roughly 100%, in percentage by volume,of the orientable, or even anisotropic particles, or even of theparticles of the first particulate fraction, belong to one and the sameshape class.

Preferably, the particles of one shape class are manufactured by thesame manufacturing process and consist of the same material.

Preferably, the smallest angle between the direction of orientation ofthe orientable particles and at least one function direction is roughlyconstant. It may be below 25°, or even below 10°, or even below 5°,preferably roughly zero. As a variant, it may be greater than 65°, oreven greater than 80°, or even greater than 85°, preferably roughlyequal to 90°.

Orientable Particles of a Material with Oriented Function

According to the invention, the ensemble of the ceramic particlescomprises more than 1%, preferably more than 2%, preferably more than3%, preferably more than 5%, by volume of the ceramic particles, oforientable ceramic particles of a material with oriented function. Theproportion of orientable ceramic particles of a material with orientedfunction is not, however, limited to these ranges and this proportionmay be greater than 10%, greater than 20%, greater than 30%, greaterthan 40%, greater than 50%, greater than 60%, greater than 70%, greaterthan 80%, or greater than 90%, or even of 100%, by volume of the ceramicparticles.

In one embodiment, the particles of the first particulate fraction, oreven the anisotropic ceramic particles, or even the orientable ceramicparticles, or even all the ceramic particles, are of a material withoriented function.

Preferably, said material with oriented function has at least oneproperty, other than mechanical, such that there is at least onedirection in which said property is at least 1.2 times, preferably 1.5times, preferably 2 times, preferably 3 times, preferably 5 times, oreven 10 times, greater than the average value of said property in theother directions.

The oriented function may notably correspond to thermal, electrical,piezoelectric or magnetic properties. Preferably, the shape of theorientable particles is selected so that the orientation of theseparticles resulting from the freezing step c) results in orienting theoriented function in a preferred direction or plane, i.e. to increase ordecrease this function in this direction or this plane.

Moreover, the number or the density of oriented particles thus allowsthe intensity of said property to be varied.

For example, there are materials with oriented function for which thethermal conductivity is different depending on the direction considered,and maximum along a particular plane, for example particles of boronnitride. Such particles may be in the form of platelets, the thermalconductivity being maximum in the general plane of the platelets. A wallconsisting of a stack of such platelets so that the planes of maximumconductivity of the particles are roughly parallel thus allows maximumdiffusion of heat in the wall along these planes.

There are also orientable particles for which the piezoelectric responseis different depending on the direction considered, and maximum along aparticular plane, notably particles of potassium sodium niobate. A wallconsisting of a stack of these particles such that the planes of maximumpiezoelectric response of the particles are roughly parallel can thusfavour this response in the wall along these planes.

Particles of the Second Particulate Fraction

The particles of the second particulate fraction may be, completely orpartially, orientable or non-orientable, anisotropic or non-anisotropic.

In one embodiment, the second particulate fraction preferably representsmore than 80%, more than 90%, or even more than 95% of the ceramicparticles.

Fraction Complementary to the Orientable Particles or to the AnisotropicParticles

The fraction of the ceramic particles complementary to the orientableparticles or to the anisotropic particles may consist, completely orpartially, of particles of the second particulate fraction, but also ofcoarser particles.

The median length of the ceramic particles of this complementaryparticulate fraction is preferably less than, preferably less than 2times, less than 5 times the median length L′₅₀ of the first particulatefraction. The quality of the stack of the orientable, preferablyanisotropic, particles is advantageously improved thereby.

In one embodiment, the fraction complementary to the orientableparticles or to the anisotropic particles consists of the secondparticulate fraction.

With the proviso that the ensemble of the ceramic particles comprisesmore than 1% of orientable ceramic particles of a material with orientedfunction, the materials constituting the other orientable, or evenanisotropic, ceramic particles, the ceramic particles of the secondparticulate fraction, the particles of the fraction complementary to theorientable particles or to the anisotropic particles and the particlesof the first particulate fraction may be of materials M_(A), M_(B),M_(C), and M_(D) respectively, which may be identical or different.

In one embodiment, the material of the ceramic particles of the secondparticulate fraction has a melting point above the sinteringtemperature. Preferably, the material M_(A) and/or the material M_(B)and/or the material M_(C) and/or the material M_(D) comprise(s), or is(are) selected from oxides, nitrides, carbides, carboxynitrides,graphite, graphene and mixtures thereof, preferably selected from groupA comprising zirconium oxide or zirconia (ZrO₂), partially stabilizedzirconium oxide, stabilized zirconium oxide, yttrium oxide (Y₂O₃), dopedyttrium oxide, preferably yttrium oxide doped with samarium oxide,titanium dioxide (TiO₂), the aluminosilicates such as mullite,cordierite (Al₃Mg₂AlSi₅O₁₈), aluminium oxide or alumina (Al₂O₃), thehydrated aluminas, and in particular boehmite, magnesium oxide (MgO),talc (Mg₃Si₄O₁₀(OH)₂), nickel oxide (NiO), the iron oxides (FeO, Fe₂O₃,Fe₃O₄), cerium oxide, doped cerium oxide, the oxides with perovskitestructure, in particular the gallates, compounds comprising lanthanum ofthe type LaAlO₃ or LaGaO₃ or La_((1−x))Sr_(x)MO₃, with 0≤x≤1 and M anelement selected from the group comprising chromium, cobalt, magnesium,iron, gadolinium, manganese and mixtures thereof; the oxides withperovskite structure doped with platinum and/or palladium and/or rhodiumand/or gold and/or silver, for example La_((1−x))Sr_(x)M_((1−y))M′_(y)O₃with 0≤x≤1, 0≤y≤0.15, M being an element selected from the groupcomprising chromium, cobalt, magnesium, iron, gadolinium, manganese andmixtures thereof, M′ being an element selected from the group comprisingplatinum, palladium, rhodium, gold, silver and mixtures thereof, thecompounds comprising titanium of the type La₄Sr₈Ti₁₁Mn_(1−x)Ga_(x)O₃₈with 0≤x≤1 and La₄Sr₈Ti_(12-n)Mn_(n)O₃₈ with 0≤n≤1, the compounds of thetype BaTiO₃, BaZrO₃, (1−x)[Pb(Mg_(1/3)Nb_(2/3))O₃]-x[PbTiO₃], with xbetween 0 and 1, Pb(Mg_(0.25)Nb_(0.75))O₃, Ba(Zn_(0.25)Nb_(0.75))O₃,Pb(Zn_(0.25)Nb_(0.75))O₃, PbTiO₃, CaCu₃Ti₄O₁₂, the compounds with astructure of the bimevox type, for example Bi₂V_(1−x)Me_(x)O_(z) with0≤x≤1, z such as to ensure electroneutrality, and Me an element selectedfrom the group comprising magnesium, aluminium, silicon, titanium,cobalt, nickel, copper, zinc, manganese, antimony, tantalum, niobium,chromium, molybdenum, tungsten, uranium and mixtures thereof, thecompounds with a structure of the lamox type, for example La₂Mo₂O₉, thecompounds with the apatite structure, for example Me′₁₀(XO₄)₆Y′₂ inwhich Me′ is a metal cation selected from the group comprising Ca²⁺,Cd²⁺, Sr²⁺, Ba²⁺, Pb²⁺, Na⁺, K⁺, cations of rare earths, preferably La³⁺and Nd³⁺, Al³⁺, U⁴⁺, Th⁴⁺, (XO₄) is an anionic group selected from PO₄³⁻, SiO₄ ⁴⁻, AsO₄ ³⁻, MnO₄ ⁻, SO₄ ²⁻, CO₃ ²⁻, HPO₄ ²⁻, SiO₄ ⁴⁻, GeO₄ ⁴⁻and mixtures thereof, and Y′ is an anion selected from F⁻, Cl⁻, OH⁻,Br⁻, I⁻, CO₃ ²⁻, O²⁻ and mixtures thereof, the compounds of typeSrCe_(1−x)M_(x)O₃ with 0≤x≤1 and M a rare earth, M preferably beingytterbium, the compounds of the type BaCe_(1−x)M_(x)O₃, with 0≤x≤1 and Ma rare earth, for example the compound BaCeO₃, the compounds of thefamily La_(x)Sr_(1−x)ScO₃ with 0≤x≤1, for example La_(0.9)Sr_(0.1)ScO₃,the zeolites of structureNa_(x1)Ca_(x2)Mg_(x3)Ba_(x4)K_(x5)Al_(x6)(Si_(x7)O_(x8)),x9H₂O, x1 to x9being positive integers or zero fulfilling the following conditions:x6>0, x7>0, x8>0, x9>0 and x1+x2+x3+x4+x5>0, (Li,Na,K)(Nb,Ta,Sb)O₃,KNbO₃ optionally doped preferably with lithium and/or tantalum and/orbarium, NaNbO₃ optionally doped preferably with lithium and/or tantalumand/or barium, (K_(0.5)Na_(0.5))NbO₃ optionally doped preferably withlithium and/or tantalum and/or barium, haematite, aluminium nitride,boron nitride, preferably hexagonal boron nitride, silicon nitride,titanium nitride, titanium carbide, silicon carbide, tungsten carbide,zirconium carbide, graphite, graphene and mixtures thereof.

Preferably, the zirconium oxide is stabilized, partially and preferablyfully, with yttrium oxide and/or with calcium oxide and/or withmagnesium oxide and/or with cerium oxide and/or with scandium oxideand/or with samarium oxide and/or with strontium oxide and/or withtitanium oxide, preferably with yttrium oxide. Preferably, the ceriumoxide is doped with samarium oxide and/or with gadolinium oxide and/orwith yttrium oxide and/or with iron oxide, preferably doped withgadolinium oxide.

In one embodiment, the material M_(A) and/or M_(B) and/or M_(C) and/orM_(D) is not magnetic, and/or the anisotropic ceramic particles, or eventhe orientable particles, or even the ceramic particles, are notcovered, even partially, with a magnetic coating.

Liquid Phase

The amount of liquid phase, or the amount of water, is preferably above50%, preferably above 60%, preferably above 70%, preferably above 80%,preferably above 90%, in percentage by volume of the slip.

The liquid phase preferably contains more than 50%, preferably more than60%, preferably more than 70%, preferably more than 80%, preferably morethan 90% of water, preferably more than 95% of water, in percentage byvolume based on the liquid phase. The liquid phase may consist of water.

In one embodiment, the liquid phase may comprise an alcohol, preferablyin an amount above 0.5%, preferably above 1%, preferably above 2%,preferably above 3%, and/or below 10%, or even below 5%, by weight basedon the weight of the liquid phase. Preferably said alcohol is selectedfrom the group comprising methanol, ethanol, tert-butanol, and mixturesthereof.

In one embodiment, the liquid phase does not comprise alcohol.

In one embodiment, the liquid phase is 2-methylpropan-2-ol.

Preferably, the liquid phase comprises a cellulose ether, especiallywhen the orientable, or even anisotropic, ceramic particles areparticles of boron nitride. Preferably, the amount of cellulose ether issuch that the ratio (weight of cellulose ether, in grams)/[(specificsurface of the ceramic particles, in m²/g)×(weight of the orientableceramic particles, in grams) is above 0.0003 g/m², above 0.0004 g/m²,preferably above 0.0005 g/m², preferably above 0.0006 g/m² and below0.004 g/m², below 0.035 g/m², preferably below 0.003 g/m², preferablybelow 0.002 g/m², or even below 0.0015 g/m². The inventors discovered,unexpectedly, that the presence of a cellulose ether makes it possibleto prepare a suspension having very low viscosities, regardless of theshear gradient.

The cellulose ether is preferably a cellulose ether of the alkyl family,preferably a methyl cellulose, or a cellulose ether of the hydroxyalkylfamily, preferably a hydroxyethyl cellulose.

The amount of cellulose ether is preferably above 0.1%, or even above0.3%, or even above 0.4% and/or below 5%, or even below 4%, or evenbelow 2.5%, or even below 2%, or even below 1.5%, or even below 1%, inpercentage by weight based on the weight of said ceramic particles.

During mixing, the pH of the slip is preferably between 3 and 12.Degradation of the cellulose ether is advantageously reduced, or eveneliminated thereby. The pH may be adjusted by adding acid(s) and/orbase(s).

The slip preferably contains at least one binder, preferably temporary.Preferably the content of binder is between 0.5 and 5 wt % based on theamount of ceramic particles. Advantageously, the mechanical strengthbefore sintering is improved thereby. The temporary bindersconventionally used in the manufacture of sintered products may be used,for example polyvinyl alcohol (PVA), polyethylene glycols (PEG).

The slip may also contain a dispersant facilitating production of ahomogeneous suspension. Preferably, the content of dispersant is between0.1 and 10 wt %, based on the amount of powder of ceramic particles. Thedispersants conventionally used in the manufacture of sintered productsby slip casting may be employed, for example the ammoniumpolymethacrylates such as Darvan C, made by the company Vanderbilt.

The slip may also contain an anti-foaming agent. Preferably the contentof anti-foaming agent is between 0.1 and 10 wt % based on the amount ofpowder of ceramic particles. The anti-foaming agents conventionally usedin the manufacture of sintered products by slip casting may be employed,for example CONTRASPUM CONC. marketed by the company Zschimmer andSchwarz.

In one embodiment, the ceramic particles, water, optional binder,optional dispersant, optional anti-foaming agent together represent morethan 80%, more than 90%, more than 95%, more than 99%, or even roughly100% of the weight of the slip.

The slip may also comprise an additive. Preferably the content ofadditive is between 0.01% and 20 wt % based on the weight of the ceramicparticles and/or of the precursors of ceramic particles. The additivemay be selected from the compounds conventionally used as antifreezes,in particular from the group consisting of sodium chloride (NaCl),glycerol, the carbohydrates such as sucrose and trehalose. Preferably,when the orientable ceramic particles are particles of boron nitride,the preferred additive is a carbohydrate, preferably sucrose. Theadditive may also be zirconium acetate.

Preferably the various constituents of the slip are added with stirring.

Mixing of the various constituents of the slip may be carried out by anytechnique known by a person skilled in the art, for example in a mixer,in a Turbulat mixer, in a drum-type ball mill, preferably of the samekind as the ceramic powder in suspension. The intensity of mixing and/orthe mixing time are preferably adjusted so as not to break theorientable particles. For this purpose, the orientable particles may beintroduced last in the previously mixed slip.

If a rotating drum grinder is used, the mixing time is preferably morethan 0.5 hour and less than 20 hours. Preferably, a rotating drumgrinder is used, the orientable particles being added to a slippreviously mixed for 24 hours, the mixing time starting from adding theorientable particles to the slip being more than 30 minutes andpreferably less than 2 hours.

Mixing may be facilitated by treating the slip with ultrasound, withenergy preferably above 70 Wh/kg of slip, preferably above 100 Wh/kg,preferably above 150 Wh/kg, while preventing the slip temperatureexceeding 30° C. A cooling system, for example water circulation, may beprovided to limit the temperature rise.

In step b), the slip is preferably poured into a mould suitable for theoriented freezing in the next step.

Preferably, a process according to the invention also comprises anoperation of removing the air bubbles, preferably before pouring theslip into the mould. The air bubbles are preferably removed by degassingunder vacuum or using ultrasound.

In step c), the slip is cooled so as to solidify the liquid phase andform crystals of solidified liquid phase. So that the directions ofgrowth of the various crystals are roughly parallel, the slip issolidified progressively by creating and then displacing, in the slip, azone with rapid thermal transition between an upstream region in whichthe liquid phase has solidified and a downstream region in which theliquid phase is still liquid. Its passage through the slip leads tosolidification of the liquid phase. That is why this zone isconventionally called the “solidification front”.

The creation and movement of a solidification front, required fororiented freezing of the slip, are techniques commonly used in the fieldof “ice templating”. This technology is a particular embodiment of thegeneral process of “freezing/removal of frozen crystals”, called “freezecasting”. Preferably, a liquid, in particular liquid nitrogen, is usedfor creating the solidification front.

Preferably, the velocity Vp of the solidification front is adjusted sothat e≤100·W1 ₅₀, preferably e<50·W1 ₅₀, preferably e<30·W1 ₅₀,preferably e<25·W1 ₅₀.

In one embodiment, the velocity Vp of the solidification front isadjusted so that W1 ₅₀≤e≤16·W1 ₅₀, preferably W1 ₅₀≤e<12·W1 ₅₀,preferably W1 ₅₀≤e≤4·W1 ₅₀. Preferably in said embodiment,

-   -   more than 90%, more than 95%, or even roughly 100% by volume of        the orientable ceramic particles, preferably anisotropic, have a        length L between 7 and 16 μm, a thickness W1 between 0.5 and 1        μm, and an elongation factor L/W1 between 10 and 20,    -   the ceramic particles represent between 8 and 11 vol % of the        volume of the slip,    -   the orientable ceramic particles, preferably anisotropic,        represent more than 90 vol % of the ceramic particles, and    -   the velocity of the solidification front is between 15 μm/s and        25 μm/s.

In one embodiment, W1 ₅₀≤e≤16·W1 ₅₀, preferably 3·W1 ₅₀≤e≤15·W1 ₅₀,preferably 5·W1 ₅₀≤e≤15·W1 ₅₀, preferably 10·W1 ₅₀≤e≤15·W1 ₅₀.Preferably in said embodiment,

-   -   more than 90%, more than 95%, or even roughly 100% by volume of        the orientable ceramic particles, preferably anisotropic, have a        length L between 7 and 16 μm, a thickness W1 between 0.5 and 1        μm, and an elongation factor L/W1 between 10 and 20,    -   the ceramic particles represent between 14 and 19 vol % of the        volume of the slip,    -   the orientable ceramic particles, preferably anisotropic,        represent more than 90 vol % of the ceramic particles, and    -   the velocity of the solidification front is between 10 μm/s and        20 μm/s.

In one embodiment, 17·W1 ₅₀≤e≤100·W1 ₅₀, preferably 20·W1 ₅₀≤e≤50·W1 ₅₀.Preferably in said embodiment,

-   -   more than 90%, more than 95%, or even roughly 100% by volume of        the orientable ceramic particles, preferably anisotropic, have a        length L between 5 and 8 μm, a thickness W1 between 0.2 μm and 1        μm, and an elongation factor L/W1 between 10 and 20,    -   the ceramic particles represent between 14 and 19 vol % of the        volume of the slip,    -   the orientable ceramic particles, preferably anisotropic,        represent more than 90 vol % of the ceramic particles, and    -   the velocity of the solidification front is between 7 μm/s and        15 μm/s.

With passage of the solidification front, the new crystals of solidifiedliquid phase are oriented, and then grow roughly in the direction ofsolidification imposed by the thermal gradient. The direction ofsolidification corresponds approximately to the direction of advance ofthe solidification front.

The size of the crystals of solidified liquid phase mainly depends onthe velocity of displacement of the solidification front and on thethermal gradient associated with this solidification front. The higherthe velocity of the solidification front, the smaller the crystals ofsolidified liquid phase.

The size of the crystals of solidified liquid phase may also be modifiedby the composition of the slip, and in particular by the optionalpresence of a binder and/or by the size of the ceramic particles.

A person skilled in the art thus knows how to adapt the process toobtain a desired wall thickness. In particular, he knows that to reducethe thickness e, it is sufficient to increase the temperature gradienton passage of the solidification front and/or increase the cooling rateand/or reduce the length of the particles in suspension and/or reducethe amount of particles in suspension in the slip, and vice versa.

Oriented freezing leads to macroscopic truncated tubular pores (exceptin particular conditions described in “Solidification of colloidalsuspensions”, Peppin et al., J. Fluid Mech. (2006), Vol. 554, pp.147-166), in contrast to pores formed by coextrusion.

When a product according to the invention is intended to be infiltratedwith an impregnating material, the truncated shape of the tubular poresimproves impregnation.

The shape of the solidification front is not limiting. In particular,the solidification front may be flat at the scale of the blockmanufactured.

The direction of displacement of the solidification front is preferablystraight, leading to crystals that are approximately rectilinear.Advantageously, it is thus possible to create long crystals ofsolidified liquid phase, roughly parallel to one another. Thesolidification of the liquid phase leads to concentration of the ceramicparticles in the spaces between the crystals of solidified liquid phase.During this movement, the particles of the second particulate fractionbecome trapped between the coarse particles, which leads to an increasein apparent density, notably after sintering.

Several solidification fronts, having identical or different thermalgradients and/or shapes, may be created and displaced, successively orsimultaneously, in identical or different directions, at identical ordifferent velocities. In particular, when the slip has been poured intoa mould, several solidification fronts may start out from differentfaces of the mould, for example starting from each face of the mould.The crystals of solidified liquid phase are then oriented from theoutside towards the centre of the block of solidified slip.

Preferably, the direction of displacement of a solidification front isroughly perpendicular to the surface from where it started.

In one embodiment, the conditions of oriented freezing are adapted toform crystals of solidified liquid phase having, in a median transverseplane, a width more than 5 times, preferably more than 10 times, or evenmore than 20 times greater than the thickness of the crystal ofsolidified liquid phase.

The crystals of solidified liquid phase then have a lamellar generalshape of small thickness, when observed in a median transverse plane.

In this embodiment, preferably more than 50%, preferably more than 70%,preferably more than 80%, preferably more than 90%, preferably more than95% by number, preferably roughly all the crystals of solidified liquidphase are roughly parallel to one another.

During the step of oriented freezing, as it moves, the solidificationfront pushes back the particles of the slip in the walls located betweenthe crystal lamellae of solidified liquid phase, thus forming, dependingon the width of said lamellae, walls that are preferably roughly flatand parallel to one another.

The shape of the crystals of solidified liquid phase depends in additionon the conditions of seeding and growth of the first crystals ofsolidified liquid phase initially formed in step c). A person skilled inthe art knows how to determine these conditions of seeding. For example,he can use a surface, starting from which seeding takes place,comprising a pattern of spaced, parallel linear reliefs, as described inthe article “Architectural Control of Freeze Cast Ceramics ThroughAdditives and Templating”, E. Munch, E. Saiz, A. P. Tomsia, S. Deville,J. Am. Ceram. Soc., Vol. 92, No. 7, pages 1534 to 1539 (2007),incorporated by reference. The crystals of solidified liquid phase thengrow in a direction that depends on the patterns of the linear reliefs.Moreover, a person skilled in the art knows how to determine the desiredthickness of the crystals of solidified liquid phase, notably bychanging the spacing between the patterns of linear reliefs. A personskilled in the art may thus partly obtain a desired shape of pores thatremain after removal of the crystals of solidified liquid phase, andnotably a flattened shape in a median cross-section.

As a variant, to obtain crystals of solidified liquid phase having alamellar shape, able after step e) to form flattened pores, a process of“freeze-tape casting”, as described in the article “Fabrication ofFunctionally Graded and Aligned Porosity in Thin Ceramic Substrates Withthe Novel Freeze-Tape Casting Process”, S. W. Sofie, J. Am. Ceram. Soc,Vol. 90, No. 7, pages 2024-2031, (2007), incorporated by reference, maybe employed.

The shape of the pore cross-section mainly depends on the velocity ofthe solidification front.

The shape of the cross-section of a pore may also be modified by thepresence of additives in the slip, as described above, as is alsodescribed in the article “Architectural Control of Freeze Cast CeramicsThrough Additives and Templating”, E. Munch, E. Saiz, A. P. Tomsia, S.Deville, J. Am. Ceram. Soc., Vol. 92, No. 7, pages 1534 to 1539 (2007),incorporated by reference.

Preferably, the whole of the slip is solidified during step c).

In step d), the block of solidified slip is removed from the mould.Preferably, the temperature conditions are adjusted to avoid any meltingof the crystals of solidified liquid phase.

In step e), the block of solidified slip is placed in conditions ofpressure and temperature leading to removal of the crystals ofsolidified liquid phase.

Preferably, removal results from sublimation of the crystals ofsolidified liquid phase. Advantageously, sublimation takes place almostwithout any displacement of the particles disposed between thesecrystals. For example, the crystals of solidified liquid phase may besublimed by heating them at very low pressure, typically at a pressurebelow 0.5 mbar.

It is also possible to melt the crystals of solidified liquid phase, andallow the resultant liquid to flow away.

The disappearance of a crystal of solidified liquid phase leaves roomfor a macroscopic pore delimited by a wall principally formed by theparticles initially in suspension in the slip, the shape of this poreroughly corresponding to the shape of the crystal removed. Thus, thecreation of elongated crystals of solidified liquid phase, roughlyparallel to one another, is what leads to the creation of tubular pores,also parallel to one another.

A macroporous preform is thus obtained.

The presence of a binder makes it possible to increase the mechanicalstrength of the macroporous preform.

Step e) is continued preferably until all the crystals of solidifiedliquid phase have been removed.

In the embodiment described above, where the block formed in step c)comprises lamellar crystals of solidified liquid phase, themanufacturing process may comprise a step e′), preferably following stepe), consisting of compressing said block in a direction roughly parallelto the direction of the thickness of the lamellar crystals of solidifiedliquid phase, so as to obtain a product having a relative density above85%, preferably above 90%, or even above 95%.

Such a step advantageously makes it possible to manufacture a denseproduct comprising oriented grains with oriented function. This denseproduct, optionally sintered respectively, has an intensity of theoriented function per unit volume of the product and mechanicalproperties (breaking stress, toughness) that are increased relative tothose of the block starting from which it was formed by compression, orrelative to a block obtained in step c) and then sintered, respectively.

As illustrated in FIGS. 30 and 31 showing a product 90 observed in amedian cross-section, during the compression step C, the walls 102consisting of orientable particles 104, located between the flattenedpores 105 resulting from the removal of the lamellar crystals oforiented liquid phase, are displaced relative to one another and getcloser together until they come in contact. This compression step thenresults in partial, or even total, removal of flattened pores, and thenonly a residual porosity 110 remains.

In other words, the dense product obtained by the compression stepconsists of a stack of walls. The thickness of the dense product 120 ispreferably more than 2 times, preferably more than 5 times, preferablymore than 10 times, preferably more than 50 times, preferably more than100 times, preferably more than 500 times, or even more than 1000 times,greater than the average thickness in a median transverse plane of awall separating two pores.

Preferably, the thickness of the dense product is above 50 μm,preferably above 100 μm, preferably above 500 μm, or even above 1 mm, oreven above 5 mm, or even above 1 cm, or even above 5 cm.

In step c) or in step d) or in step e), a portion of the blockcomprising more than 50%, preferably more than 60%, preferably more than70%, preferably more than 80%, preferably more than 90%, preferably morethan 95%, preferably roughly 100% of lamellar crystals of solidifiedliquid phase, preferably roughly parallel to one another, may beselected and then extracted, for example by cutting out or stamping. Itis then possible to perform the operation of compression described aboveon said portion of block, in a direction roughly parallel to thedirection of the thickness of the lamellar crystals of solidified liquidphase.

In step f), the macroporous preform is arranged in such a way that itcan be heated. Any binder present is then removed. The plateau time, thetemperature and the atmosphere for the binder removal treatment aredetermined in relation to the nature of the binder or binders used.

Preferably, a process comprises a sintering step g), leading to anincrease in mechanical strength. The resultant porous sintered productadvantageously has good mechanical strength, even after removing thebinder. The plateau time, the temperature and the atmosphere forsintering are determined as a function of the nature and characteristicsof the product to be manufactured. These parameters are well known by aperson skilled in the art.

In a preferred embodiment, binder removal and sintering are carried outduring the same thermal treatment, steps f) and g) being combined.

In a preferred embodiment, step e′) of compression of the block may becarried out before and/or together with the step of binder removal f)and/or the sintering step g). Preferably, the step of binder removal f)and/or the sintering step g) are then carried out by the method ofsintering under pressure (“Hot Pressing”, HP) or by the SPS (“SparkPlasma Sintering”) method, which are familiar to a person skilled in theart. Sintering then allows rigid bonding of the walls that were broughtinto contact by the compression step.

Sintering may also be carried out following placement of the macroporouspreform in its operating position, for example if a product according tothe invention is used as catalyst support in a reactor operating at hightemperature.

Sintering may transform the morphology of the fine grains (correspondingto the particles of the second particulate fraction) disposed betweenthe orientable, in particular anisotropic grains. Under the effect ofthis transformation, the fine grains may in particular coalesce with theorientable grains, for example so as to form larger orientable grains,improve the stacking of the grains and reduce the interstices betweensaid grains. This notably results in remarkable apparent density andmechanical properties.

FIG. 8b illustrates the structure of the wall resulting from thepresence of the particles of the second particulate fraction. It showsthat after sintering, the particles of the second particulate fractionhave coalesced with the platelets initially present to form platelets,sometimes with shapes complementary to that of the initial platelets.The residual microporosity (black spots) is advantageously greatlyreduced thereby.

This wall structure contrasts with that in FIG. 6, for which the slipcontained practically no particles of the second particulate fraction.

In step h), the porous product may be machined by any technique known bya person skilled in the art. Preferably, the porous product is machinedin order to remove the transition zone corresponding to the start of thesolidification front and the establishment of stable solidificationconditions, the solidification conditions being called “stable” when thegrowth rate of the crystals of solidified liquid phase is roughlyconstant.

Impregnation may be carried out by any technique known by a personskilled in the art. Preferably the impregnation is an impregnation usinga liquid medium.

The impregnating material may be selected from ceramics, metals, organicmaterials and mixtures thereof, notably selected from:

-   -   the materials of group A above,    -   a catalytic coating comprising or consisting of a catalyst        material selected from        -   metals, preferably iron (Fe), cobalt (Co), nickel (Ni),            molybdenum (Mo), copper (Cu), ruthenium (Ru), rhodium (Rh),            platinum (Pt), palladium (Pd), gold (Au), silver (Ag),            iridium (Ir), osmium (Os), rhenium (Re), and mixtures            thereof;        -   oxides, preferably the oxides of scandium (Sc), of titanium            (Ti), of vanadium (V), of chromium (Cr), of cobalt (Co), of            copper (Cu), of palladium (Pd), of molybdenum (Mo), of iron            (Fe), of nickel (Ni), of tungsten (W), of rhenium (Re),            oxides with perovskite structure, oxides with fluorite            structure, zeolites, oxides of lanthanides, preferably CeO₂,            and mixtures thereof;        -   the carbides, the oxycarbides of formulae            (carbide)_(1−x)O_(x)., with 0<x<1;        -   and mixtures thereof;    -   aluminium, copper, alloys of aluminium and of copper,    -   polymers, and notably resins    -   and mixtures thereof.

Preferably, the impregnating material is different from the material ofthe product according to the invention into which it is infiltrated.

Impregnation may lead to simple coating on the surface of the truncatedtubular pores or to partial or complete filling of said pores.

The particular shape of the macroscopic tubular pores means they can beinfiltrated very efficiently by an impregnating material, in particularto constitute a composite material. This efficiency is remarkable whenthe ensemble of particles of the impregnating material, generally insuspension, have a median length less than 0.1 times the averageequivalent diameter of the wide openings of the truncated tubular pores,and preferably less than 0.1 times the average equivalent diameter ofthe narrow openings of said pores. The median length of the ensemble ofparticles of the impregnating material may typically be between 0.01 μmand 4 μm. The truncated tubular pores are preferably open at both ends,further facilitating penetration of the impregnating material.

Preferably, when a product according to the invention is impregnatedwith an impregnating material, penetration of the impregnating materialtakes place via the wide openings of the pores.

A process according to the invention makes it possible to manufacture aproduct in a ceramic material, which is therefore particularly able towithstand high temperatures and thermal shocks.

Product According to the Invention

A product according to the invention may be manufactured by a processaccording to the invention.

The materials constituting the orientable, or even anisotropic ceramicgrains, the fine ceramic grains (i.e. corresponding to the particles ofthe second particulate fraction) and the grains of the fractioncomplementary to the orientable grains or to the anisotropic grains maybe of materials M_(A), M_(B) and M_(C), respectively, which may beidentical or different.

In one embodiment, the material of the fine ceramic grains has a meltingpoint above the sintering temperature.

Preferably, material M_(A) and/or material M_(B) and/or material M_(C)comprise(s), or is (are) selected from oxides, nitrides, carbides,carboxynitrides and mixtures thereof. They may in particular be selectedfrom group A.

In one embodiment, the product comprises less than 10 vol % of finegrains, or even less than 5%, or even less than 3%, or even less than1%, or even practically no fine grains, the particles of the secondparticulate fraction having been transformed into coarser grains duringsintering.

The shape and the dimensions of the ceramic grains, in particular of theorientable, or even anisotropic ceramic grains, may correspond to thatof the ceramic particles, in particular orientable, or even anisotropicceramic particles of the slip. The amounts of ceramic grains and oforientable, or even anisotropic ceramic grains, by volume based on thegrains making up a wall, may correspond to the amounts of ceramicparticles and of orientable, or even anisotropic ceramic particlesrespectively, by volume based on the volume of the particles of the slipand by volume based on the volume of the ceramic particles of the slip,respectively.

Preferably, the fraction of the ceramic grains that are not anisotropic,or even that are not orientable, has a median length less than ten timesthe median length of the anisotropic, or even orientable ceramic grainsrespectively, especially if the ensemble of ceramic grains in said wallscomprises less than 80%, in percentage by volume, of anisotropic ororientable ceramic grains, respectively.

Truncated Tubular Pores

Preferably, said truncated tubular pores are roughly adjacent to oneanother so that the transverse planes defining their respective mediancross-sections roughly coincide with the average median transverseplane. The average equivalent diameter of the median cross-sections forthe ensemble of said truncated tubular pores may then advantageouslyeasily be determined by analysis of an image of a section of the productalong this average median transverse plane.

The average equivalent diameter of the median cross-sections of thetruncated tubular pores is preferably above 0.5 μm, preferably above 1μm, or even above 2 μm, or even above 5 μm and/or preferably below 400μm, preferably below 300 μm, preferably below 270 μm, preferably below200 μm, or even below 150 μm, or even below 100 μm, or even below 50 μm,or even below 15 μm, or even below 10 μm.

In a preferred embodiment, in the average median transverse plane, atleast 50% by number of the truncated tubular pores (considering theensemble of truncated tubular pores visible in the average mediantransverse cutting plane) have a convexity index Ic greater than 87%,the convexity index of a pore being equal to the ratio Sp/Sc of thesurface areas Sp and Sc delimited by the perimeter and by the convexenvelope of said pore, respectively. In other words, these truncatedtubular pores are approximately smooth.

The shape of the truncated tubular pores is preferably such that, in theaverage median transverse cutting plane:

-   -   at least 60%, preferably at least 70%, by number of the pores        have a convexity index Ic and/or a solidity index Is greater        than 87%, and/or    -   at least 40%, preferably at least 44%, preferably at least 54%,        by number of the pores have a convexity index Ic and/or a        solidity index Is greater than 88%, and/or    -   at least 30%, preferably at least 36%, preferably at least 40%,        preferably at least 44%, preferably at least 50%, by number of        the pores have a convexity index Ic and/or a solidity index Is        greater than 89%, and/or    -   at least 24%, preferably at least 30%, preferably at least 36%,        preferably at least 40%/a, preferably at least 44%, preferably        at least 50%, by number of the pores have a convexity index Ic        and/or a solidity index Is greater than 90%, and/or    -   at least 20%, preferably at least 24%, preferably at least 30%,        preferably at least 35%, preferably at least 40%, preferably at        least 45%, by number of the pores have a convexity index Ic        and/or a solidity index Is greater than 91%, and/or    -   at least 16%, preferably at least 20%, preferably at least 24%,        preferably at least 30%0, preferably at least 40%, by number of        the pores have a convexity index Ic and/or a solidity index Is        greater than 92%, and/or    -   at least 4%, preferably at least 8%, preferably at least 10%,        preferably at least 20%, by number of the pores have a convexity        index Ic and/or a solidity index Is greater than 93%.

The cross-section of the truncated tubular pores may or may not becircular. In particular, it may be polygonal, and notably convexhexagonal.

In one embodiment, the cross-section of a truncated tubular pore isflattened. Such a flattened pore may be obtained by removing a crystalof solidified liquid phase of lamellar shape formed in step c) of theprocess according to the invention. Preferably, more than 50%, or evenmore than 70%, or even more than 90%, or even more than 95%, or evenmore than 99%, or even roughly 100% by number of the truncated tubularpores are flattened.

The geometry of the cross-section of the truncated tubular pores may beroughly constant, regardless of the cross-section considered. Forexample, a pore may have a cross-section of convex hexagonal generalshape, regardless of the transverse cutting plane considered, the areaof this section being variable.

Preferably, at least 70%, preferably at least 80%, preferably at least90% by number of the pores are truncated tubular pores opening at theirtwo ends with large and narrow openings, respectively. These pores arecalled “through-pores”. It is thus easier to impregnate them, notablywith a catalyst. When they are used as catalyst support, the catalysisreactions are also improved thereby.

More preferably, the ratio of the average equivalent diameter (averagedfor the ensemble of said truncated tubular through-pores) of the narrowopenings to the average equivalent diameter (averaged for the ensembleof said truncated tubular through-pores) of the wide openings is below0.99, preferably below 0.95, or even below 0.90, or even below 0.85, oreven below 0.80, or even below 0.75.

Walls

Preferably more than 40%, more than 70%, more than 90%, or even roughly100% of the volume of walls of a product according to the invention hasa roughly identical structure, in particular having one or more of thecharacteristics described below.

Preferably, a wall between said truncated tubular pores comprises morethan 10%, preferably more than 20%, preferably more than 30%, preferablymore than 50%, preferably more than 70%, preferably more than 80%,preferably more than 90% of orientable, preferably anisotropic ceramicgrains. In one embodiment, the wall is constituted almost entirely oforientable, or even anisotropic ceramic grains.

In one embodiment, the orientable ceramic grains, or even theanisotropic ceramic grains, or even the ceramic grains, are not covered,even partially, with a magnetic coating.

Preferably, more than 50%, or even more than 60%, or even more than 70%,or even more than 80%, or even more than 90%, or even more than 95%, oreven roughly 100% of the weight of the walls consists of grains,preferably ceramic.

Arrangement of the Ceramic Grains

The orientable ceramic grains are preferably arranged in an orderedmanner. Preferably they have one or more preferential orientations, i.e.their orientation is not random. In particular, they may be stacked inthe form of layers, preferably roughly parallel to the outside surfaceof the wall considered, in the proximity of which they extend.

In one embodiment, the concentration of orientable ceramic grainsarranged in an ordered manner is higher at the periphery of said walls(i.e. in the proximity of the outside surfaces of the walls in contactwith the internal volumes of the truncated tubular pores) than at thecentre of said walls (in the proximity of their median planes).

These characteristics may be demonstrated by an image analysis of across-section of the wall considered, said image having at least 10grain boundaries, for example using the Fiji software and the criterion“directionality”. The orientation of the ceramic grains according to theinvention leads to a peak of higher intensity on the histogram producedby the software (giving the quantity of grain boundaries as a functionof the direction (in degrees)). This peak may be approximated by aGaussian, the “dispersion” being equal to twice the standard deviationof this Gaussian.

Preferably, according to the invention, the dispersion (value alsocalled “dispersion” in the software) is below 30°, preferably below 20°,preferably below 15°.

The histogram produced by the software may comprise several peaks.

Preferably, the area covered by the grain boundaries corresponding tothe peak of higher intensity, as a percentage of the area analysed bythe software (the value called “Amount” in the software) is above 2%,preferably above 5%, or even above 10%, or even above 20%, or even above40%, or even above 50%, or even above 60%, or even above 70%, or evenabove 80%.

In one embodiment, the wall considered comprises a peripheral stratum,i.e. defining, at least partly, the outside surface of the wall, thisstratum consisting of a layer of orientable, preferably anisotropic,ceramic grains or by a stack of at least 2 layers of orientable,preferably anisotropic, ceramic grains, preferably 2 to 20, or even from2 to 10, or even from 2 to 8, or even from 2 to 7, layers of orientable,preferably anisotropic ceramic grains, a “layer of grains” consisting ofa plurality of adjacent grains that are not superposed.

In one embodiment, the wall considered comprises two peripheral strataeach defining, at least partly, an outside surface of the wall, thesestrata each consisting of a layer of orientable, preferably anisotropic,ceramic grains or by a stack of at least 2 layers of orientable,preferably anisotropic, ceramic grains, preferably from 2 to 20, or evenfrom 2 to 10, or even from 2 to 8, or even from 2 to 7, layers oforientable ceramic grains, preferably anisotropic.

In one embodiment, the wall considered comprises a central stratum,extending between said two peripheral strata, and consisting of anensemble of grains whose arrangement is not ordered.

In one embodiment, the ceramic grains are grains of boron nitride andthe wall considered comprises a peripheral stratum, i.e. defining, atleast partly, the outside surface of the wall, this stratum consistingof a layer of orientable, preferably anisotropic ceramic grains, or by astack from 2 to 10, preferably from 2 to 8, preferably from 2 to 7,layers of orientable, preferably anisotropic grains of boron nitride.

The thickness of the central stratum may represent less than 30%, lessthan 10%, less than 5% of the thickness of the wall. The wall may alsonot comprise a central stratum.

FIG. 3 shows schematically a cross-section of a wall 10 illustratingsuch a structure. The wall 10, of thickness “e”, comprises two outsidesurfaces 12 a and 12 b defining the internal volumes of two truncatedtubular pores 14 a and 14 b, respectively.

The grains 16 constituting the wall 10 are platelets which form twoperipheral strata 18 a and 18 b, defining the two outside surfaces 12 aand 12 b, respectively, and a central stratum 18 c.

Each of the two peripheral strata 18 a and 18 b consists of a pluralityof layers 20 of roughly parallel grains, in this case seven layers. Inthese layers, the grains are arranged flat. The plane of the layers isroughly parallel to the direction of displacement of the solidificationfront D.

In the central stratum 18 c, the particles do not have a preferentialorientation.

Employing a process according to the invention, it is possible to modifythe thickness e, and therefore modify the microstructure of the wall, bychanging the velocity of the solidification front Vp. Especially whenthe particles are platelets, for example of the type used for theexamples, the inventors found that the amount of platelets that may takea preferred orientation under the effect of passage of thesolidification front is limited. In particular, the thickness of eachperipheral stratum does not exceed about 8 layers of platelets of boronnitride. Thus, if the thickness e is less than the thickness of 16platelets, practically all the platelets become oriented in planesroughly parallel to the direction of displacement of the solidificationfront and become stacked in the form of layers. If the thickness e isgreater than the thickness of 16 platelets, a central stratum appears,in which the platelets are no longer oriented. Increasing or reducingthe wall thickness thus makes it possible to increase or reduce thepercentage of the thickness of the wall consisting of oriented plateletsof boron nitride.

In one embodiment, the wall does not comprise a central stratum andpractically all the orientable, preferably anisotropic ceramic grainsare arranged in an ordered manner. Preferably said wall is made up ofmore than 20 layers, or even of more than 30 layers of orientable,preferably anisotropic ceramic grains.

The thickness “e” of the wall and the orientable ceramic grains arepreferably such that e<25·L₅₀, preferably e<20·L₅₀, preferably e<16·L₅₀,preferably e≤15·L₅₀.

In one embodiment, the wall comprises a single stratum consisting of alayer of orientable, preferably anisotropic, ceramic grains or by astack of at least 2 layers of orientable, preferably anisotropic,ceramic grains, preferably from 2 to 10, or even from 2 to 20, or evenfrom 2 to 50 layers of orientable, preferably anisotropic ceramicgrains.

Preferably at least 70%, preferably at least 80%, preferably at least90%, preferably at least 95%, preferably substantially 100% by number ofthe grains of said single stratum are roughly parallel to one anotherand roughly parallel to the outside surface of said wall.

Preferably, the orientable ceramic grains constituting the singlestratum are platelets or rodlets.

Preferably, over the width of a median cross-section of a pore, thenumber of superposed grains (according to the thickness) is roughlyconstant. Preferably, the number of superposed grains varies by plus orminus 10% relative to the average number of superposed grains.

Preferably, when observed in a median cross-section, a truncated tubularpore has a flattened section, and more than 80% by number of the grainsof a portion of wall extending between two flattened adjacent pores arestacked flat on top of one another.

A product comprising such walls displays an optimized response of theoriented function.

In a wall located between the truncated tubular pores of a productaccording to the invention, preferably more than 10%, preferably morethan 20%, preferably more than 30%, preferably more than 50%, preferablymore than 70% preferably more than 80%, preferably more than 90% bynumber of the grains are orientable, preferably anisotropic ceramicgrains.

In a wall located between the truncated tubular pores of a productaccording to the invention, the areal fraction of the orientable ceramicgrains, measured on a median cross-section, preferably represents morethan 100%, preferably more than 20%, or even more than 30% of the totalarea of said wall. In a preferred embodiment, the complement to saidareal fraction of the orientable ceramic grains is the porosity.

In one embodiment, the walls (i.e. the material between the truncatedtubular pores) of the product according to the invention are porous (theporosity of the walls being typically greater than or equal to 10 vol%). The open porosity of the walls between the truncated tubular poresis preferably above 30%, or even above 40% and/or below 90%, preferablybelow 80%, preferably below 70%, or even below 60%, or even below 50%.Advantageously, the mechanical properties are improved thereby.

EXAMPLES

The examples not according to the invention are referenced with (*).

The products in the examples were manufactured by a process according tothe invention.

The following raw materials were used:

-   -   Powder of platelets of hexagonal boron nitride Très BN PUHP        3016, marketed by the company Saint-Gobain, having a median size        equal to 16 μm and a specific surface equal to 2 m²/g,    -   Powder of platelets of hexagonal boron nitride Très BN PUHP 500,        marketed by the company Saint-Gobain, having a median size equal        to 6 μm and a specific surface equal to 7 m²/g,    -   Alumina powder TM-DAR Taimicron marketed by the company Krahn        Chemie GmbH,    -   Powder of alumina platelets RonaFlair White Sapphire marketed by        the company Merck,    -   Colloidal solution of silica Nexsil 20K marketed by the company        NYACOL,    -   Powders of K₂CO₃, Na₂CO₃, Nb₂O₅, Bi₂O₃ marketed by the company        Sigma-Aldrich,    -   Powder of copper oxide (CuO) marketed by Sigma-Aldrich,    -   Powder of calcium nitrate marketed by the company Sigma-Aldrich,    -   Polyethylene glycol PEG20M marketed by the company Merck,    -   Solution of Darvan 811 marketed by the company Vanderbilt,    -   Powder of Darvan 7NS marketed by the company VanderBilt,    -   Powder of Tylose H4000P2 marketed by Shin-Etsu,    -   Solution of polyethylene glycol 4000, or PEG4000, with a        proportion of active substance equal to 32%,    -   Sucrose powder marketed by Sigma-Aldrich,    -   NaCl powder marketed by Sigma-Aldrich,    -   Zirconium acetate, diluted to 22 wt % in acetic acid marketed by        the company Saint-Gobain.

The following methods were used for characterization:

The average equivalent diameter of the cross-sections of the pores ismeasured by the following method:

The sample to be analysed is infiltrated with a resin, for example anepoxy resin. A section is prepared, at mid-length of the truncatedtubular pores, perpendicularly to the direction of solidification, andthen polished in order to obtain a good surface state, said polishingbeing carried out at least with a grade 1200 paper, preferably with adiamond paste. Images are recorded using a scanning electron microscope(SEM), preferably in a mode using backscattered electrons (BSE mode) inorder to obtain a very good contrast between the ceramic phase and theresin. Each image has at least 1280×960 pixels, excluding the scale bar.The magnification used is such that the width of the image is between 50times and 100 times the average pore size. A first image may be recordedbased on a visual estimate of the average pore size.

The average pore size is determined by analysis of these images by theerosion/dilatation method described in “Characterization of themorphology of cellular ceramics by 3D image processing of X-raytomography”, Maire et al., J. Eur. Ceram. Soc., 27[4] 1973-1981 (2007).

The thickness of the walls, e, of a product is measured by the followingmethod. If the product is a non-sintered product, a sample of saidproduct is broken in a direction perpendicular to the direction of thelength of the truncated tubular pores. At least a portion of the samplemust have a surface not modified by an external action after rupture, toavoid altering the orientation of the grains. If the product is asintered product, then a slice of said product to be analysed is cutperpendicularly to the direction of the length of the truncated tubularpores. Images are recorded using a scanning electron microscope (SEM).Each image has at least 1280×960 pixels, excluding the scale bar. Themagnification is such that the width of the image allows between 2 and50 pores to be imaged.

The average thickness of the walls is then measured by analysis of theseimages using the Fiji software, plotting lines delimiting the wallslaterally and then using the tool “Analyse>Measure” of said software;the column “length” of the result table gives the average thickness ofthe walls. The correspondence between pixel and unit of length may beobtained beforehand using the tool “Set Scale” and measuring the numberof pixels of the scale bar.

The thickness W1, length L or D, and elongation factor R of theparticles, as well as the average thickness W1 ₅₀ and the averageelongation factor Rm of the powder of particles are measured by thefollowing method. Some powder of particles is suspended in ethanol,thoroughly dispersing the particles. This suspension is then spread on aconductive support, such as carbon adhesive tape used in electronicimaging. At least 5 images are recorded using a scanning electronmicroscope (SEM), each image having as a minimum 1280×960 pixels,excluding the scale bar. The magnification is such that the width of theimage makes it possible to visualize between 2 and 20 individualparticles, i.e. not agglomerated. If this is not the case, it isnecessary to begin again with a suspension having a lower ratio ofvolume of particles to volume of ethanol. The image must have particleswhose thickness appears as roughly parallel to the plane of imaging.

The thickness of the particles, W1, is then measured by analysis of saidimages using the Fiji software, plotting lines delimiting the particlesand then using the tool “Analyse>Measure” of said software. The column“length” in the result table gives the average thickness of the walls.The correspondence between pixel and unit of length may be obtainedbeforehand using the tool “Set Scale” and measuring the number of pixelsof the scale bar. The average thickness of the particles of the powder,W1 ₅₀, is the mean value of the measured thicknesses W1.

The length of each particle is also measured. The elongation factor, R,equal to the length of the particle divided by the width of saidparticle, is calculated, as well as the average elongation factor, Rm,of the powder of particles, equal to the arithmetic mean of theelongation factors R.

The alignment of the grains in the walls of a product is measured by thefollowing method. If the product is a non-sintered product, a sample ofsaid product is broken in a direction perpendicular to the direction ofthe length of the truncated tubular pores. At least a portion of thesample must have a surface not modified by an external action afterrupture, in order to avoid altering the orientation of the grains. Ifthe product is a sintered product, then a slice of said product to beanalysed is cut perpendicularly to the direction of the length of thetruncated tubular pores, and then undergoes a thermal treatment with theaim of revealing the grain boundaries. Images are recorded using ascanning electron microscope (SEM). Each image has at least 1280×960pixels, excluding the scale bar. The magnification is such that theheight of the image is equal to the size of a wall of thickness e. Theorientation of the grains is then measured by means of the tool“Analyse>Directionality” of the Fiji software, selecting the method ofmeasurement “Local Gradient Orientation”, “Nbins” equal to 90 and“Histogram Start” equal to −90°. The two quantities in thischaracterization are the “Dispersion”, which quantifies the angulardispersion of the alignment in the image and the quantity “amount”,which quantifies the fraction of the image having a preferentialalignment.

The absolute density of the material making up the product is the ratioequal to the mass of dry matter of said material after grinding tofineness such that practically no closed pore remains, divided by thevolume of this mass after grinding. It may be measured with a heliumpycnometer.

The open porosity in the walls is measured by mercury porosimetry. Asintered sample of known mass and absolute density is put in apenetrometer suitable for the size and the volume of the porosity to bemeasured. The minimum pressure to be applied to the mercury is adjustedso as to be able to force the mercury into pores with sizes at leastfifteen times less than the median length of the grains in the sample.As shown in FIG. 29, in which the abscissa shows the diameter of thepores in microns and the ordinate shows the volume of mercury introducedin mL/g, a main peak is obtained corresponding to the truncated tubularmacroporosity and other peaks whose sum corresponds to the volume of theopen pores in the walls. The volume of mercury used for filling the openporosity in the walls is calculated from the following formula:Volume of mercury in the open porosity of the walls=Total volume ofmercury introduced−Volume of mercury V₁ introduced in the samplecorresponding to the main peak.

The percentage open porosity in the walls of the sample may then becalculated from the following formula:100×Volume of mercury in the open porosity of the walls/[(Volume ofmercury in the open porosity of the walls+(Mass of the sample/Absolutedensity of the sample)].

The relative apparent density of the walls is equal to (100−openporosity in the walls).

The products in examples 1, 2, and 3 are boron nitride products,manufactured by the following process.

In step a), the mixtures given in Table 1 (in percentages by volumebased on the total volume of each of the slips prepared) were stirred ina beaker using a magnetic stirrer for 5 hours.

TABLE 1 Example 1 2 3 Très BN PUHP 3016 18.5 Ceramic powder Très BN PUHP500 18.6 Très BN PUHP 3008 17.4 PEG 4000 solution 0.8 0.9 0.8 Ethanol2.7 2.7 2.1 Tylose H 4000 P2 0.8 0.8 0.8 Deionized water 77.2 77.0 78.9vol % of ceramic particles based on the 18.5 18.6 17.4 volume of theslip % of orientable particles, based on the Roughly Roughly Roughlyvolume of ceramic powder 100 100 100 Median length L′₅₀ of theorientable ceramic 16 6 8 particles (μm) Average elongation factor Rm ofthe powder 16 24 16 of orientable particles Average thickness of theorientable ceramic 1 0.25 0.54 particles W1₅₀ (μm)

Then each slip obtained was treated ultrasonically, as follows: thevessel containing the suspension is put in a water-filled tank of aDigital Sonifier 250 ultrasonic apparatus, marketed by the companyBranson. The intensity of the ultrasound was set to 50% of the maximumintensity, i.e. setting at a power equal to 100 W. Ultrasound wasapplied for 1.5 s, then stopped for 1.5 s, this cycle being repeated for14 minutes, after which the water in the tank reached a temperature of30° C. The energy applied to the suspension was between 150 and 160Wh/kg of suspension.

The suspension was then stirred with a magnetic stirrer for 12 hours.

In step b), each slip was poured into a mould, the bottom of which wasin contact with a copper plate cooled by a refrigerated liquid. Thecooling rate of the copper plate controls the velocity of displacementof the solidification front Vp in the suspension.

In step c), for examples 1 and 2, the slip was submitted to orientedfreezing with a freezing rate equal to −1° C./min or a velocity ofdisplacement of the solidification front roughly equal to 15 μm/s, andfor example 3, the slip was frozen at a rate of −0.5° C./min, leading toa velocity of displacement of the solidification front roughly equal to8 μm/s. After mould release in step d), sublimation in step e) wascarried out by placing the block of frozen slip in a lyophilizer for 48h at a pressure of 0.42 mbar.

The products in examples 1, 2 and 3 did not undergo other steps.

The alumina product in example 4 was produced as follows: theconstituents shown in Table 2 below were mixed for 6 hours in a drumgrinder so as to form a slip:

TABLE 2 vol % as percentages of the volume of the slip ConstituentsExample 4(*) First particulate fraction: RonalFlair White 1.3 Sapphirepowder Second particulate fraction: TM-DAR powder 11.9 PEG 20M 1.5Darvan 811 2.6 Sucrose 3.3 Nexsil 20K 0.6 Calcium nitrate 0.1 Deionizedwater 78.7 vol % of the ensemble of ceramic particles, 13.2 based on thevolume of slip vol % represented by the first particulate fraction, 10based on the volume of ceramic powder Median length L′₅₀ of the firstparticulate 9 fraction (μm) Average elongation factor Rm of the first 18particulate fraction Average thickness W1₅₀ of the first particulate 0.5fraction (μm) vol % represented by the second particulate fraction, 90based on the volume of ceramic powder Median length D₅₀ of the secondparticulate 0.1 fraction (μm)

Steps b) to e) of preparation of the product in example 4 are identicalto those for preparation of the products in examples 1, 2 and 3, apartfrom in step c) where the slip was submitted to oriented freezing with afreezing rate equal to −1° C./min, or a velocity of displacement of thesolidification front roughly equal to 15 μm/s.

The product in example 4 was then submitted to a sintering step with thefollowing cycle:

Temperature rise of 50° C./h up to 490° C., plateau of 1 h at 490° C.,temperature rise of 30° C./h up to 550° C., plateau of 30 minutes at550° C., temperature rise of 300° C./h up to 1550° C., plateau of 1.5 hat 1550° C., temperature decrease at a rate of 300° C./h to roomtemperature.

After making samples of the product in example 4, these were submittedto a thermal treatment according to the following cycle: temperaturerise of 300° C./h up to 1450° C., plateau of 20 minutes at 1450° C.,temperature decrease at a rate of 300° C./h to room temperature.

The results obtained are shown in Table 3 below:

TABLE 3 Example 1 2 3 4(*) Thickness of the walls, e (μm) 21 28 29 7Amount (%) 79 63 70 53 Dispersion (°) 20.92 19.91 23.38 11.29

The products in examples 1 to 4 have a remarkable amount of orientablegrains that are oriented in a preferential direction.

The product in example 5 was prepared as follows.

A powder of KNN (K_(0.5)Na_(0.5)NbO₃) was synthesized starting from theprecursors K₂CO₃, Na₂CO₃, Nb₂O₅ by mixing K₂CO₃, Na₂CO₃ and Nb₂O₅ inmolar proportions 1:1:2 in ethanol in a drum grinder for three days. Thesuspension obtained was then dried until the solvent had evaporatedcompletely and was then submitted to the following cycle of thermaltreatment: temperature rise at 4° C./min up to 800° C., plateau at 800°C. for 6 hours, then temperature decrease at a natural rate. The powderobtained is in the form of roughly spherical particles with medianlength D₅₀ equal to 0.5 μm.

A powder of NN (Na_(0.5)NbO₃) was synthesized starting from theprecursors Na₂CO₃, Nb₂O₅, Bi₂O₃ by the method of microcrystallinetopochemical conversion: the precursors Na₂CO₃, Nb₂O₅ and Bi₂O₃ weremixed in molar proportions 1.75:2.5:1.25, then NaCl was added at aweight ratio NaCl:mixture (Na₂CO₃, Nb₂O₅ and Bi₂O₃) equal to 2:1. Thewhole was then put in ethanol, then ground in a drum grinder for 15 h,and finally mixed for 3 hours in a Turbulat mixer. The mixture obtainedwas then dried until the solvent had evaporated completely, then treatedthermally in the following cycle: temperature rise at 3° C./min up to700° C., then temperature rise at 4° C./min up to 1125° C., plateau at1125° C. for 6 hours, then temperature decrease at a rate equal to 1.8°C./min. The powder of Bi_(2.5)Na_(3.5)Nb₅O₁₈ obtained was then washedseveral times with hot water to remove the salt NaCl added previously.Na₂CO₃ in molar proportions 1:0.75 relative to Bi_(2.5)Na_(3.5)Nb₅O₁₈was mixed with salt NaCl at a weight ratio salt:mixture (Na₂CO₃,Bi_(2.5)Na_(3.5)Nb₅O₁₈) equal to 1.5:1. The mixture obtained was put inethanol and ground in a drum grinder for 14 hours, then the particles ofBi_(2.5)Na_(3.5)Nb₅O₁₈ were added to the suspension, and the whole wasground in a rotating drum grinder for 5 hours. The mixture obtained wasthen dried until the solvent had evaporated completely, then treatedthermally in the following cycle: temperature rise at 4° C./min up to975° C., plateau at 975° C. for 6 hours, then temperature decrease at arate equal to 1.8° C./min. The powder obtained was washed several timeswith hot water to remove the NaCl added previously, then it was washedfour times with nitric acid to remove the residual bismuth. The finalpowder of NaNbO₃ is in the form of a powder of platelets whose medianlength L′₅₀ is equal to 15 μm and average thickness W1 ₅₀ is equal to1.5 μm.

In step a), the constituents shown in Table 4 below were then mixed for12 hours in a drum grinder without powder of NN, then 1 h in a drumgrinder with the powder of NN, so as to form a slip:

TABLE 4 vol % as percentages of the volume of the slip ConstituentsExample 5 Second particulate fraction: KNN powder 12.69 Firstparticulate fraction: NN powder 1.44 CuO powder 0.05 Darvan 7NS 0.16 PEG20M 2.54 Sucrose 2.50 Deionized water 80.62 vol % of the ensemble ofceramic particles, 14.22 based on the volume of slip vol % representedby the first particulate fraction, 10 based on the volume of ceramicpowder Median length L′₅₀ of the first particulate 15 fraction (μm)Average elongation factor Rm of the first 10 particulate fractionAverage thickness W1₅₀ of the first particulate 1.5 fraction (μm) vol %represented by the second particulate fraction, 89.7 based on the volumeof ceramic powder Median length D₅₀ of the second particulate 0.5fraction (μm)

In step b), the slip was poured into a mould, the bottom of which was incontact with a copper plate cooled by a refrigerated liquid. The coolingrate of the copper plate controls the velocity of displacement of thesolidification front Vp in the suspension.

In step c), the slip was submitted to oriented freezing with a freezingrate equal to −1° C./min, or a velocity of displacement of thesolidification front roughly equal to 15 μm/s.

After mould release in step d), sublimation in step e) was carried outby putting the block of frozen slip in a lyophilizer for 48 h at apressure of 0.42 mbar.

The macroporous preform obtained was then put in an alumina crucible,closed, put on a bed of KNN powder and was then submitted to a sinteringstep with the following cycle: temperature rise at a rate equal to 50°C./h up to 550° C., plateau of 1 hour at 550° C., temperature rise at arate equal to 4° C./h up to 1115° C., plateau of 4 hours at 1115° C.,temperature rise at a rate equal to 1° C./h up to 1125° C., plateau of 3hours at 1125° C., temperature decrease at a rate equal to 300° C./h toroom temperature.

The product in example 5 obtained is a macroporous product ofK_(0.4)Na_(0.6)NbO₃, having walls consisting of roughly cubic grains.

The product according to example 3 was then impregnated with a siliconeresin TSE3033 by an impregnation process under vacuum. The resin plusthe sample were put inside a polymer mould and then held under vacuum of0.11 bar for 10 minutes. The vacuum was broken and then restored for aperiod of 20 minutes. The body thus impregnated with resin was heated ina stove at 110° C. for 2 h in order to complete the crosslinking of thesilicone.

The product in the comparative example was made by mixing 18 vol % ofpowder Très BN PUHP 3008 in the resin used for impregnating the productaccording to example 3. The next steps of the process for making thecomparative example were identical to those of the impregnated productin example 3, but without a freezing step, and therefore also without astep of removal of crystals. The amount of particles of boron nitrideused in the comparative example is above the percolation threshold.These particles therefore form a continuous network of particlesimmersed in the resin used.

Thermal diffusivity was then measured by the flash method on each of thetwo products described above. The following Table 5 presents the resultsobtained:

TABLE 5 Product from the Impregnated comparative product Example examplefrom example 3 Thermal diffusivity at 20° C. (mm²/s) 0.35 1.03

The impregnated product in example 3, according to the invention, has athermal diffusivity more than 3 times higher than that of the product inthe comparative example, in which the particles are oriented randomly.

As is now clear, the process according to the invention makes itpossible to obtain porous products with truncated tubular macroporeswhose walls display a remarkable orientation of function.

Advantageously, the open wall porosity may also be particularly low.

Of course, the invention is not limited to the embodiments given asexamples. In particular, several different ceramic powders could bemixed in the slip in step a).

The invention claimed is:
 1. Process for manufacturing a product,optionally sintered, said process comprising the following steps: a)preparing a slip comprising an ensemble of ceramic particles insuspension in a liquid phase, the ensemble of ceramic particlescomprising orientable ceramic particles and optionally nonorientableceramic particles, the nonorientable ceramic particles defining afraction, the ensemble of ceramic particles representing more than 4%and less than 50% of the volume of the slip and comprising, inpercentage by volume based on the ensemble of ceramic particles, morethan 1% of orientable ceramic particles of a material with orientedfunction, the fraction of the nonorientable ceramic particles having amedian length ten times less than the median length of the orientableceramic particles L₅₀ if the ensemble of ceramic particles comprisesless than 80%, in percentage by volume, of orientable ceramic particles,b) optionally, pouring the slip into a mould and/or removing air bubblescontained in the slip, c) oriented freezing of the slip by displacementof a solidification front so as to form a block of frozen slip, thevelocity Vp of the solidification front being less than the velocity ofencapsulation of the ceramic particles Vc and adjusted so as to formcrystals of solidified liquid phase separated by walls with an averagethickness “e” greater than or equal to the average thickness of theorientable ceramic particles W1 _(50;) d) optionally, removing saidblock from the mould, e) removing the crystals of solidified liquidphase from said block, optionally removed from the mould, so as toobtain a macroporous preform comprising macropores, a shape of theorientable particles being determined so that the orientation of theorientable particles under the effect of the freezing in step c)results, in the macroporous preform, in an intensity of said functionwhich is variable in a direction under consideration, f) optionally,removing a binder from the macroporous preform obtained at the end ofstep e), g) optionally, sintering the macroporous preform so as toobtain a sintered product, this step g) being obligatory if, in step a),the amount of orientable ceramic particles of a material with orientedfunction is less than 80%, in percentage by volume based on the ensembleof the ceramic particles; h) optionally, machining and/or impregnatingsaid sintered product.
 2. Process according to claim 1, wherein thematerial with oriented function is selected from the group consisting ofhexagonal boron nitride, graphite, graphene,(1−x)[Pb(Mg_(1/3)Nb_(2/3))O₃]−x[PbTiO₃], with x between 0 and 1, PbTiO₃,and (Li,Na,K)(Nb,Ta,Sb)O₃.
 3. Process according to claim 1, wherein adirection is determined and then the shape of the orientable particlesis selected in relation to the orientation of the function, so that theoriented freezing makes it possible to obtain properties whose intensityis variable in said direction.
 4. Process according to claim 1, whereinthe ensemble of ceramic particles comprises, in percentage by volumebased on the ensemble of the ceramic particles, a first particulatefraction consisting of orientable particles, of a material with orientedfunction, having a median length L′₅₀ and representing more than 1% ofthe ceramic particles, in percentage by volume based on the ensemble ofceramic particles; and a second particulate fraction having a medianlength D₅₀ at least ten times less than L′₅₀ and representing more than5% of the ceramic particles, in percentage by volume based on theensemble of ceramic particles; the first and second particulatefractions together representing more than 80% of the ensemble of ceramicparticles, in percentage by volume.
 5. Process according to claim 4,wherein the first particulate fraction represents more than 5% and lessthan 15% of the volume of the ceramic particles, and the particles ofthe first particulate fraction are of the material with orientedfunction, and the first and second particulate fractions togetherrepresent more than 95% of the volume of the ensemble of the ceramicparticles, and the granulometric distribution of the ceramic particlesis bimodal, the two principal modes corresponding to the first andsecond particulate fractions, respectively, the process comprising thesintering step g).
 6. Process according to claim 4, wherein the firstparticulate fraction represents more than 90% of the volume of theceramic particles, and the particles of the first particulate fractionare of a material with oriented function, and the first and secondparticulate fractions together represent more than 95% of the volume ofthe ensemble of ceramic particles, and the granulometric distribution ofthe ceramic particles is bimodal, the two principal modes correspondingto the first and second particulate fractions, respectively.
 7. Processaccording to claim 4, wherein a material constituting the orientableceramic particles, and/or the ceramic particles of the secondparticulate fraction and/or the particles of a fraction complementary tothe orientable particles is selected from oxides, nitrides, carbides,carboxynitrides and mixtures thereof.
 8. Process according to claim 7,wherein the material is selected from the group consisting ofun-stabilized or partially stabilized or stabilized zirconium oxide(ZrO₂), un-doped or doped yttrium oxide (Y₂O₃), titanium dioxide (TiO₂),aluminosilicates, aluminium oxide (Al₂O₃), magnesium oxide (MgO), talc(Mg₃Si₄O₁₀(OH)₂), nickel oxide (NiO), iron oxides (FeO, Fe₂O₃, Fe₃O₄),un-doped or doped cerium oxide, oxides with perovskite structureun-doped or doped with platinum and/or palladium and/or rhodium and/orgold and/or silver, compounds comprising titanium of a typeLa₄Sr₈Ti₁₁Mn_(1 −x)Ga_(x)O₃₈ with 0 ≤x≤1 and La₄Sr₈Ti_(12 −n)Mn_(n)O₃₈with 0 ≤n≤1, compounds with a structure of the bimevox type, compoundswith a structure of the lamox type, compounds with an apatite structure,aluminium nitride, boron nitride, silicon nitride, titanium nitride,titanium carbide, silicon carbide, tungsten carbide, zirconium carbide,and mixtures thereof.
 9. Process according to claim 1, wherein theoriented function corresponds to a thermal, electrical, piezoelectric ormagnetic property.
 10. Process according to claim 1, wherein theorientable ceramic particles are boron nitride platelets, each platelethaving a thermal conductivity in the main plane of the platelet which isgreater than the thermal conductivity in the thickness of the platelet.11. Process according to claim 1, wherein the orientable ceramicparticles are anisotropic particles or multifaceted particles havingmore than two facets.
 12. Process according to claim 1, wherein morethan 50% of the orientable particles belong to one and the same shapeclass, in percentage by volume.
 13. Process according to claim 1,wherein the ensemble of ceramic particles comprises, in percentage byvolume based on the ensemble of the ceramic particles, more than 80% oforientable ceramic particles.
 14. Process according to claim 1, wherein,in step c), the conditions of oriented freezing are adjusted to formcrystals of solidified liquid phase, having, in a median transverseplane, a width more than 5 times greater than the thickness of thecrystal of solidified liquid phase.
 15. Process according to claim 14,wherein more than 50% of the crystals of solidified liquid phase areroughly parallel to one another.
 16. Process according to claim 14,comprising a step e′), consisting of compressing the block in adirection roughly parallel to the direction of the thickness of thecrystals of solidified liquid phase, so as to obtain a block having arelative density above 85%.
 17. Process according to claim 16, thecompression step being carried out before and/or jointly with the stepof binder removal f) and/or the sintering step g).
 18. Process accordingto claim 1, comprising, at step a), replacing partially or completelythe ceramic particles with equivalent amounts of precursors that aretransformed into ceramic particles so as to obtain said ensemble ofceramic particles before step c), and/or replacing partially orcompletely the ceramic particles with equivalent amounts of particles ofthe same shape of a ceramic precursor that is transformed into ceramicin step f) or g).